Novel microbiocides

ABSTRACT

Compounds of the formula (I), in which the substituents are as defined in claim  1  are suitable for use as microbiocides.

The present invention relates to novel microbiocidally active, inparticular fungicidally active, ethyloxy amides. It further relates tointermediates used in the preparation of these compounds, tocompositions which comprise these compounds and to their use inagriculture or horticulture for controlling or preventing infestation ofplants by phytopathogenic microorganisms, preferably fungi.

Similar compounds are also known in other fields of technology, forexample, the use of aminoacetonitroles as insecticides is described inWO 03/004474.

It has been found that novel ethyloxy amides have microbiocidalactivity. The present invention thus provides compounds of the formula I

whereinA is a 5-membered heterocyclic ring containing one to three heteroatoms,each independently selected from oxygen, nitrogen and sulphur, theheterocyclic ring being substituted by the groups R₅, R₆ and R₇;R₅, R₆ and R₇ are each, independently, hydrogen, halogen, cyano, nitro,C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy(C₁-C₄alkyl) or C₁-C₄halogenalkoxy(C₁-C₄alkyl), provided thatat least one of R₅, R₆ and R₇ is not hydrogen;R₁, R₂, R₃ and R₄ independently of each other are hydrogen, halogen,C₁-C₆alkyl, C₁-C₆halogenalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy,C₁-C₆halogenalkoxy, C₁-C₆alkylthio or C₁-C₆halogenalkylthio;or R₁ and R₂ together are a C₂-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups;or R₁ and R₃ together are a C₁-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups;or R₃ and R₄ together are a C₂-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups;R₁₅ is hydrogen or C₃-C₇cycloalkyl;B is phenyl, naphthyl or a 5- to 10-membered heteroaromatic ring systemcontaining one to three heteroatoms, each independently selected fromoxygen, nitrogen and sulphur, the phenyl, naphthyl or 5- to 10-memberedheteroaromatic ring system being substituted by one or more substituentsR₈;each substituent R₈ independently of each other is halogen, C₁-C₆alkoxy,—C(O)H, C₁-C₆alkylcarbonyl, amino, C₁-C₆alkylamino, di-C₁-C₆alkyl-amino,C₁-C₆alkylcarbonylamino, C₁-C₆haloalkoxy, C₁-C₆haloalkylthio, cyano,nitro, —C(R^(a))═N(OR^(b)), —N═C(R^(e))—N(R^(f))₂, C₁-C₆alkyl, which isunsubstituted or substituted by one or more substituents R₉,C₂-C₆alkenyl, which is unsubstituted or substituted by one or moresubstituents R₉, C₂-C₆alkynyl, which is unsubstituted or substituted byone or more substituents R₉, C₂-C₆alkenyloxy, which is unsubstituted orsubstituted by one or more substituents R₉, C₃-C₆cycloalkyl, which isunsubstituted or substituted by one or more substituents R₉,C₆-C₁₄bicycloalkyl, which is unsubstituted or substituted by one or moresubstituents R₉, phenyl, which is unsubstituted or substituted by one ormore substituents R₉, or phenyloxy, which is unsubstituted orsubstituted by one or more substituents R₉;each R₉ is independently of each other halogen, nitro, C₃-C₆cycloalkyl,C₁-C₆alkoxy, C₁-C₆halogenalkoxy, C₁-C₆alkylthio, C₁-C₆halogenalkylthio,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenyl, halophenyl,tri-C₁-C₆alkyl-silyl or —C(R^(c))═N(OR^(d));each R^(a), R^(c), R^(e) and R^(f) is independently of each otherhydrogen or C₁-C₆alkyl;each R^(b) and R^(d) is independently of each other C₁-C₆alkyl;and tautomers/isomers/enantiomers of these compounds.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, n-butyl, sec-butyl,iso-butyl or tent-butyl. Alkoxy, alkenyl and alkynyl radicals arederived from the alkyl radicals mentioned. The alkenyl and alkynylgroups can be mono- or di-unsaturated.

In the context of the present invention “substituted by one or moresubstituents” in the definition of the substituents, means typically,depending on the chemical structure of the substituents, monosubstitutedto seven-times substituted, preferably monosubstituted to five-timessubstituted, more preferably mono-, double- or triple-substituted.

The cycloalkyl groups occurring in the definitions of the substituentsare, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Halogen is generally fluorine, chlorine, bromine or iodine, preferablyfluorine, bromine or chlorine. This also applies, correspondingly, tohalogen in combination with other meanings, such as halogenalkyl orhalogenalkoxy.

Halogenalkyl groups preferably have a chain length of from 1 to 4 carbonatoms. Halogenalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy,isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.Halogenalkoxy is, for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy andtrifluoromethoxy.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

Halogenphenyl is preferably phenyl substituted by 1, 2 or 3 halogenatoms, for example 4-chloro-phenyl.

R₁₅ as C₃-C₇cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl or cycloheptyl, preferably cyclopropyl.

In the context of the present invention a “5- or 6-membered heterocyclicring containing one to three heteroatoms, each independently selectedfrom oxygen, nitrogen and sulphur” preferably means pyrazolyl(especially pyrazol-4-yl), thiazolyl (especially thiazol-5-yl), pyrrolyl(especially pyrrol-3-yl), 1,2,3 triazolyl, oxazolyl (especiallyoxazol-5-yl), pyridyl (especially pyrid-3-yl) or 2,3dihydro-[1,4]oxathiinyl (especially 2,3 dihydro-[1,4]oxathiin-5-yl).

The compounds of formula I can occur in different isomeric forms; theinvention covers all those isomers and mixtures thereof. The compoundsof the formula I may occur in different tautomeric forms. For example,compounds of formula I, wherein R₁₅ is hydrogen, exist in the tautomericforms I_(I) and I_(II):

The invention covers all those tautomeric forms and mixtures thereof.

In a preferred group of compounds, A is A₁

in whichR₁₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl;R₁₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₁₈ is hydrogen, halogen or cyano;

or A is A₂

in whichR₂₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₂₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl;

or A is A₃

in whichR₃₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl;R₃₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₃₈ is hydrogen, halogen or cyano;

or A is A₄

in whichR₄₆ and R₄₇ independently of one another are halogen, cyano, nitro,C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl.

Within said preferred group of compounds, further preferably A is A₁.

Within said preferred group of compounds, further preferably A is A₂.

Within said preferred group of compounds, further preferably A is A₃.

Within said preferred group of compounds, further preferably A is A₄.

In a particular preferred group of compounds A is A₁, wherein R₁₈ ishydrogen. In another particular preferred group of compounds A is A₁,wherein R₁₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl, preferablyC₁-C₄halogenalkyl; even more preferably R₁₆ is selected from CF₂H andCF₃, R₁₇ is C₁-C₄alkyl; preferably methyl; and R₁₈ is hydrogen orhalogen, preferably hydrogen. In one embodiment, R₁₆ is CF₂H, R₁₇ ismethyl and R₁₈ is hydrogen. In another particular preferred group ofcompounds A is A₂, wherein R₂₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl; andR₂₇ is C₁-C₄alkyl.

In yet another particular preferred group of compounds A is A₃, whereinR₃₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl; R₃₇ is C₁-C₄alkyl; and R₃₈ ishydrogen or halogen.

In yet another particular preferred group of compounds A is A₄, whereinR₄₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl; and R₄₇ is C₁-C₄alkyl.

In yet another particular preferred group of compounds A is A₄, whereinR₄₆ halogenmethyl, preferably R₄₆ is selected from CF₃, CF₂H and CFH₂;and R₄₇ is C₁-C₄alkyl.

in whichR₁₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl;R₁₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₁₈ is hydrogen, halogen or cyano;

or A is A₂

in whichR₂₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₂₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl;

or A is A₃

in whichR₃₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl;R₃₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₃₈ is hydrogen, halogen or cyano;

or A is A₄

in whichR₄₆ and R₄₇ independently of one another are halogen, cyano, nitro,C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl.

In a preferred group of compounds, R₁, R₂, R₃ and R₄ independently ofeach other are hydrogen or C₁-C₆alkyl; or R₁ and R₂ together are aC₂-C₅alkylene group; or R₁ and R₃ together are a C₁-C₅alkylene group; orR₃ and R₄ together are a C₂-C₅alkylene group.

In a further preferred group of compounds, R₁, R₂, R₃ and R₄independently of each other are hydrogen or C₁-C₆alkyl; more preferablyR₁ and R₂ independently of each other are C₁-C₆alkyl; and R₂ and R₄ areeach hydrogen. In a yet further preferred group of compounds, R₁ standsfor C₁-C₆alkyl, preferably methyl; and R₂, R₃ and R₄ are each hydrogen.

In another further preferred group of compounds, R₁ and R₂ together area C₂-C₅alkylene group, preferably ethylene; and R₃ and R₄ are bothhydrogen.

In another further preferred group of compounds, R₁ and R₃ together area C₁-C₅alkylene group, preferably methylene; and R₂ and R₄ are bothhydrogen.

In another further preferred group of compounds, R₁, R₂, R₃ and R₄ areall hydrogen.

Preferably R₁₅ is hydrogen.

In a preferred group of compounds, B is phenyl, naphthyl or a 5-, 6-, 9-or 10-membered heteroaromatic ring system containing one to threeheteroatoms, each independently selected from oxygen, nitrogen andsulphur, the phenyl, naphthyl or 5-, 6-, 9- or 10-memberedheteroaromatic ring system being substituted by one or more substituentsR₈;

In a preferred group of compounds, B is selected from the followinggroups:

in which R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ each independently of each otherstands for hydrogen, halogen, C₁-C₆alkoxy, —C(O)H, C₁-C₆alkylcarbonyl,amino, C₁-C₆alkylamino, di-C₁-C₆alkyl-amino, C₁-C₆alkylcarbonylamino,C₁-C₆haloalkoxy, C₁-C₆haloalkylthio, cyano, nitro, —C(R^(a))═N(OR^(b)),—N═C(R^(e))—N(R^(f))₂,C₁-C₆alkyl, which is unsubstituted or substituted by one or moresubstituents R₉,C₂-C₆alkenyl, which is unsubstituted or substituted by one or moresubstituents R₉,C₂-C₆alkynyl, which is unsubstituted or substituted by one or moresubstituents R₉,C₂-C₆alkenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉,C₃-C₆cycloalkyl, which is unsubstituted or substituted by one or moresubstituents R₉,C₆-C₁₄bicycloalkyl, which is unsubstituted or substituted by one or moresubstituents R₉,phenyl, which is unsubstituted or substituted by one or moresubstituents R₉, orphenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉;each R₉ is independently of each other halogen, nitro, C₃-C₆cycloalkyl,C₁-C₆alkoxy, C₁-C₆halogenalkoxy, C₁-C₆alkylthio, C₁-C₆halogenalkylthio,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenyl, halophenyl,tri-C₁-C₆alkyl-silyl or —C(R^(c))═N(OR^(d));each R^(a), R^(c), R^(e) and R^(f) is independently of each otherhydrogen or C₁-C₆alkyl;each R^(b) and R^(d) is independently of each other C₁-C₆alkyl;provided that at least one of R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ is nothydrogen.

Preferably, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ each independently of each otherstands for hydrogen, halogen, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₆haloalkylthio, —C(R^(a))═N(OR^(b)), C₁-C₆alkyl, which isunsubstituted or substituted by one or more substituents R₉,C₂-C₆alkenyl, which is unsubstituted or substituted by one or moresubstituents R₉, C₂-C₆alkynyl, which is unsubstituted or substituted byone or more substituents R₉, phenyl, which is unsubstituted orsubstituted by one or more substituents R₉; and each R₉ is independentlyof each other halogen or C₁-C₆alkoxy; provided that at least one of R₁₀,R₁₁, R₁₂, R₁₃ and R₁₄ is not hydrogen.

More preferably, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ each independently of eachother stands for hydrogen, halogen, C₁-C₆alkyl or C₁-C₆haloalkyl;provided that at least one of R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ is nothydrogen.

In a preferred group of compounds, B is selected from B₁, B₂, B₃, B₄,B₂₀, B₂₁, B₂₂, B₂₃, B₂₄, B₂₅, B₂₆, B₂₇, B₂₈, B₂₉ and B₃₀. Morepreferably, B is selected from B₁, B₂, B₃, B₄, B₂₀, B₂₁, B₂₂, B₂₃ andB₂₄. Even more preferably, B is B₁, B₂, B₃ or B₄. In one embodiment B isB₁.

In another embodiment B is B₂, B₃ or B₄. In yet another embodiment B isB₂. In yet another embodiment B is B₃. In yet another embodiment B isB₄.

In yet another embodiment B is B₂₀, B₂₁, B₂₂, B₂₃ or B₂₄. In yet anotherembodiment B is B₂₀ or B₂₁. In yet another embodiment B is B₂₀. In yetanother embodiment B is B₂₁.

In yet another embodiment B is B₂₂, B₂₃ or B₂₄. In yet anotherembodiment B is B₂₂.

In yet another embodiment B is B₂₃. In yet another embodiment B is B₂₄.

In yet another embodiment B is B₂₅, B₂₆, B₂₇, B₂₈, B₂₉ or B₃₀. In yetanother embodiment B is B₂₅. In yet another embodiment B is B₂₆. In yetanother embodiment B is B₂₇. In yet another embodiment B is B₂₈. In yetanother embodiment B is B₂₉. In yet another embodiment B is B₃₀.

In a preferred group of compounds, B is B₁

in which R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ each independently of each otherstands for hydrogen, halogen, C₁-C₆alkoxy, —C(O)H, C₁-C₆alkylcarbonyl,amino, C₁-C₆alkylamino, di-C₁-C₆alkyl-amino, C₁-C₆alkylcarbonylamino,C₁-C₆haloalkoxy, C₁-C₆haloalkylthio, cyano, nitro, —C(R^(a))═N(OR^(b)),—N═C(R^(e))—N(R^(f))₂,C₁-C₆alkyl, which is unsubstituted or substituted by one or moresubstituents R₉,C₂-C₆alkenyl, which is unsubstituted or substituted by one or moresubstituents R₉,C₂-C₆alkynyl, which is unsubstituted or substituted by one or moresubstituents R₉,C₂-C₆alkenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉,C₃-C₆cycloalkyl, which is unsubstituted or substituted by one or moresubstituents R₉,C₆-C₁₄bicycloalkyl, which is unsubstituted or substituted by one or moresubstituents R₉,phenyl, which is unsubstituted or substituted by one or moresubstituents R₉, orphenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉;each R₉ is independently of each other halogen, nitro, C₃-C₆cycloalkyl,C₁-C₆alkoxy, C₁-C₆halogenalkoxy, C₁-C₆alkylthio, C₁-C₆halogenalkylthio,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenyl, halophenyl,tri-C₁-C₆alkyl-silyl or —C(R^(c))═N(OR^(d));each R^(a), R^(c), R^(e) and R^(f) is independently of each otherhydrogen or C₁-C₆alkyl;each R^(b) and R^(d) is independently of each other C₁-C₆alkyl;provided that at least one of R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ is nothydrogen.

In a preferred group of compounds, B is B₁, in which R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ each independently of each other stands for hydrogen, halogen,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆haloalkylthio, —C(R^(a))═N(OR^(b)),C₁-C₆alkyl, which is unsubstituted or substituted by one or moresubstituents R₉, C₂-C₆alkenyl, which is unsubstituted or substituted byone or more substituents R₉, C₂-C₆alkynyl, which is unsubstituted orsubstituted by one or more substituents R₉, phenyl, which isunsubstituted or substituted by one or more substituents R₉;

phenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉; and each R₉ is independently of each other halogen orC₁-C₆alkoxy;provided that at least one of R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ is nothydrogen.

In a further preferred group of compounds, B is B_(1A)

in which R₁₀, R₁₂ and R₁₄ each independently of each other stands forhydrogen, halogen, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆haloalkylthio,—C(R^(a))═N(OR^(b)), C₁-C₆alkyl, which is unsubstituted or substitutedby one or more substituents R₉, C₂-C₆alkenyl, which is unsubstituted orsubstituted by one or more substituents R₉, C₂-C₆alkynyl, which isunsubstituted or substituted by one or more substituents R₉, phenyl,which is unsubstituted or substituted by one or more substituents R₉;phenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉; and each R₉ is independently of each other halogen orC₁-C₆alkoxy; provided that at least one of R₁₀, R₁₂ and R₁₄ is nothydrogen.

Further preferred are compounds, wherein B is B_(1A), in which R₁₀, R₁₂and R₁₄ each independently of each other stands for hydrogen, halogen,C₁-C₆alkyl or C₁-C₆haloalkyl;

provided that at least one of R₁₀, R₁₂ and R₁₄ is not hydrogen.

In one embodiment, R₁₀ and R₁₂ each independently of each other standsfor halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; and R₁₄ stands for hydrogen,halogen, C₁-C₆alkyl or C₁-C₆haloalkyl.

In a further embodiment, R₁₀ and R₁₂ each independently of each otherstands for halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; and R₁₄ stands forhydrogen.

In yet a further embodiment, R₁₀, R₁₂ and R₁₄ each independently of eachother stands for halogen, C₁-C₆alkyl or C₁-C₆haloalkyl.

In yet a further embodiment, R₁₀ and R₁₄ each independently of eachother stands for halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; and R₁₂ standsfor hydrogen, halogen, C₁-C₆alkyl or C₁-C₆haloalkyl.

In yet a further embodiment, R₁₀ and R₁₄ each independently of eachother stands for halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; and R₁₂ standsfor hydrogen.

In yet a further embodiment, R₁₀ stands for halogen, C₁-C₆alkyl orC₁-C₆haloalkyl; and R₁₂ and R₁₄ both are hydrogen.

In yet a further embodiment, R₁₂ stands for halogen, C₁-C₆alkyl orC₁-C₆haloalkyl; and R₁₀ and R₁₄ both are hydrogen.

In a further preferred group of compounds, B is B_(1B)

in which R₁₁, R₁₂ and R₁₃ each independently of each other stands forhydrogen, halogen, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆haloalkylthio,—C(R^(a))═N(OR^(b)), C₁-C₆alkyl, which is unsubstituted or substitutedby one or more substituents R₉, C₂-C₆alkenyl, which is unsubstituted orsubstituted by one or more substituents R₉, C₂-C₆alkynyl, which isunsubstituted or substituted by one or more substituents R₉, phenyl,which is unsubstituted or substituted by one or more substituents R₉;phenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉; and each R₉ is independently of each other halogen orC₁-C₆alkoxy; provided that at least one of R₁₁, R₁₂ and R₁₃ is nothydrogen.

Further preferred are compounds, wherein B is B_(1B), in which R₁₁, R₁₂and R₁₃ each independently of each other stands for hydrogen, halogen,C₁-C₆alkyl or C₁-C₆haloalkyl;

provided that at least one of R₁₁, R₁₂ and R₁₃ is not hydrogen.

In one embodiment, R₁₁ and R₁₃ each independently of each other standsfor halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; and R₁₂ stands for hydrogen,halogen, C₁-C₆alkyl or C₁-C₆haloalkyl.

In a further embodiment, R₁₁ and R₁₃ each independently of each otherstands for halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; and R₁₂ stands forhydrogen.

In a further embodiment, R₁₁ and R₁₂ each independently of each otherstands for halogen, C₁-C₆alkyl or C₁-C₆haloalkyl; and R₁₃ stands forhydrogen.

In a further embodiment, R₁₁, R₁₂ and R₁₃ each independently of eachother stands for halogen, C₁-C₆alkyl or C₁-C₆haloalkyl.

If R₁ is different from R₂, the S-enantiomer is preferred.

The preparation of the compounds of formula I wherein R₁₅ is hydrogen isdescribed below. The compounds of formula I, wherein R₁₅ isC₃-C₇cycloalkyl can be prepared analogously.

Compounds of formula I may be prepared by reacting a compound of formulaII

in which B, R₁, R₂, R₃ and R₄ are as defined under formula I; with acompound of formula III

A-C(═O)—R*  (III),

in which A is as defined under formula I, and R* is halogen, hydroxy orC₁₋₆ alkoxy, preferably chloro, in the presence of a base, such astriethylamine, Hunig base, sodium bicarbonate, sodium carbonate,potassium carbonate, pyridine or quinoline, but preferablytriethylamine, and in a solvent, such as diethylether, TBME, THF,dichloromethane, chloroform, DMF or NMP, for between 10 minutes and 48hours, preferably 12 to 24 hours, and between 0° C. and reflux,preferably 20 to 25° C.

When R* is hydroxy, a coupling agent, such asbenzotriazol-1-yloxytris(dimethylamino)phosphoniumhexafluorophosphate,bis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride (BOP-Cl),N,N′-dicyclohexylcarbodiimide (DCC) or 1,1′-carbonyl-diimidazole (CDI),may be used.

Intermediates of the formula II, in which B, R₁, R₂, R₃ and R₄ are asdefined under formula I; may be prepared according to the followingreaction schemes (schemes 1 to 5) or in analogy to those reactionschemes.

Intermediates of formula IIb

in which B is as defined under formula I and R₁, R₃ and R₄ independentlyof each other are hydrogen, C₁-C₆ alkyl, C₁-C₆ halogenalkyl, C₃-C₆cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆ alkoxy, C₁-C₆ halogenalkoxy, C₁-C₆ alkylthio or C₁-C₆halogenalkylthio; or R₁ and R₃ together are a C₂-C₅alkylene group, whichis unsubstituted or substituted by one or more C₁-C₆alkyl groups; or R₃and R₄ together are a C₂-C₅alkylene group, which is unsubstituted orsubstituted by one or more C₁-C₆alkyl groups; may be prepared asdescribed in reaction scheme 1.

Intermediates of formula IIe, wherein R₁₅ is C₃-C₇cycloalkyl can be forexample prepared as shown in Scheme 1a:

In Scheme 1a, the substituent n signifies 1, 2, 3, 4 or 5. Analogousprocesses for the preparation of a compound of formula IIe, wherein R₁₅is C₃-C₇cycloalkyl are described in J. Het. Chem., 1983, p. 1031-6; J.Am. Soc., 2004, p 5192-5201 and Synth. Commun. 2003, p 3419-25.

Intermediates of formula IV, in which B, R₁, R₃ and R₄ are as definedunder formula IIb, can be prepared by a Williamson reaction of a hydroxyderivative of formula VI, in which B is as defined under formula IIb,with a α-halogen carbonyl compound of formula V, in which R₁, R₃ and R₄are as defined under formula IIb. Said alkylation reaction may beperformed in the presence of a base. Suitable bases include metalhydroxides and/or carbonates such as lithium hydroxide, cesiumcarbonate, potassium carbonate, potassium hydroxide, sodium hydroxide ormetal hydrides, such as sodium hydride and lithium hydride orcesiumfluoride. Suitable solvents include ketones, such as acetone andmethyl ethyl ketone, and other solvents, such as N,N-dimethylformamide,dimethylacetamide and nitriles, such as acetonitrile and propionitrile.The reaction temperature can vary within wide limits, but typically isfrom ambient temperature to the boiling point of the reaction mixture.

Amines of formula IIb can then be prepared from compounds of formula IVby reductive amination with an excess of ammonium halide (X⁻ is halide)or acetate salt (X⁻ is acetate) in the presence of a 1-10 equivalents ofhydride reducing reagent such as sodium or tetrabutyl cyanoborohydrideor sodium triacetoxyborohydride. The reaction can be performed in proticsolvents, such as alcohols methanol, ethanol, isopropanol, tert-butanoland the like, or in aprotic solvents, such as tetrahydrofuran ordichloromethane. An acid catalyst such as HCl or p-toluenesulfonic acidcan be added portionwise in order to maintain a pH of 3-5 as determinedby pH-meter or indicator dye, such as bromocresol green or methylorange. The reaction temperature typically lies in the range of −5° C.to 60° C.

Alcohols of formula VIII, in which B, R₁, R₃ and R₄ are as defined underformula IIb, are available by ring opening of an epoxyde of formula VII,in which R₁, R₃ and R₄ are as defined under formula IIb, while using thehydroxy derivative of formula VI. The ring opening reaction may beperformed in the presence of a catalyst. Suitable catalysts includebases, such as amines like pyridine, tri-ethanolamine and the like, ormetal hydroxides and/or carbonates such as lithium hydroxide, cesiumcarbonate, potassium carbonate, potassium hydroxide, sodium hydroxide ormetal hydrides, such as sodium hydride and lithium hydride orcesiumfluoride as well as Lewis acids, such astetramethylammoniumchlorid. Suitable solvents include alcohols, such asethanol, isopropanol, tert-butanol and the like, ketones, such asacetone and methyl ethyl ketone, and other solvents, such asN,N-dimethylformamide, dimethylacetamide and nitriles, such asacetonitrile and propionitrile. The reaction temperature can vary withinwide limits, but typically is from ambient temperature to the boilingpoint of the reaction mixture.

The ketone intermediates of formula IV may then be prepared by oxidizingthe corresponding alcohols of formula VIII. Advantageous oxidationprocedures can be based on sulphur based oxidation agents (in theliterature referred to, for example, as Swern-oxidation orPfizer-Moffat-oxidation), metal based oxidation agents or hydrogenperoxide in the presence of metal catalysts, such as Na₂WO₄ (c.f. e.g.R. Noyori, Bull. Chem. Soc. Jpn. 1999, 72, 2287-2306).

An alternative access to the compounds of formula IIb (not using theketone intermediate of formula IV) is also described in scheme 2. Saidalternative access uses phthalimide derivatives.

Phthalimide derivatives of formula X, in which B, R₁, R₃ and R₄ are asdefined under formula IIb, can be directly prepared by the Gabriel typesynthesis reaction—as described by Mitsunobu (O. Mitsunobu, Synthesis,1981, 1-28)—from the alcohol of formula VIII and phthalimide in thepresence of 1-2 equivalents of triphenylphosphine and 1-2 equivalentsdialkylazodicarboxylate, such as diethylazodicarboxylate ordiisopropylazodicarboxylate. The reaction is generally run in an inertsolvent, such as tetrahydrofurane or dichloromethane, at a temperaturerange of 0° C. to 80° C.

The removal of the phthalimide protection group being present in thecompounds of formula X to form the desired compounds of formula IIb canbe effected by hydrazinolysis or other methods set out in theliterature, such as those referenced in Greene, T. W. Protective Groupsin Organic Synthesis; J. Wiley & Sons: New York, (1991); Chapter 7.

The phthalimide derivatives of formula X can also be prepared from thealcohols of formula VIII via compounds of formula IX, in which B, R₁, R₃and R₄ are as defined under formula IIb, and LG stands for a leavinggroup. Typical leaving groups are chloride, bromide, iodide,(methylsulfonyl)oxy or [(4-methylphenyl)sulfonyl]oxy. In such areaction, the leaving group LG is displaced in the presence of an acidacceptor, which can be a tertiary amine, such as triethylamine, analkoxyde, such as tertiary-butoxyde, or a carbonate, such as potassiumcarbonate. The displacements can be carried out in polar aproticsolvents, such as dimethylformamide or dimethylsulfoxide, ethersolvents, such as tetrahydrofurane or dioxane, or protic solvents, suchas ethanol. Reaction temperature typically lies in the range of from 20°C. to 150° C.

The phthalimide derivatives of formula X can also be prepared by anotherapproach: phthalimide-protected β-amino alcohols of formula XI, in whichR₁, R₃ and R₄ are as defined under formula IIb, can be transformed intothe phthalimide derivatives of formula X by a substitution reaction ofthe hydroxy group while using the hydroxy derivatives of formula VIfollowing the Mitsunobu-procedure (described in: Kenny, J. A., Synlett,1999, (10), 1615-1617).

The compounds of formula XI can be synthesized from an amino alcohol offormula XII, in which R₁, R₃ and R₄ are as defined under formula IIb, byreacting with phthalic anhydride (as described in: Bose, A. K., J. Org.Chem., 1958, 23, 1335-1338).

Yet another access to the phthalimide derivatives of formula X is thetransformation of the compounds of formula XI into compounds of formulaXIII, in which R₁, R₃ and R₄ are as defined under formula IIb, and LG isa leaving group as defined under formula IX, by standard methods for theconversion of alcohols to halides (as described in: March, J. AdvancedOrganic Chemistry; J. Wiley & Sons: New York, (1992); 4^(th) Ed, pp498-499). The compounds of the formula XIII can then be transformed intothe compounds of formula X while using the displacement conditionsdescribed above for the transformation of the compounds of formula IXinto the compounds of formula X.

Intermediates of formula IIc

in which B is as defined under formula I and R₁, R₃ and R₄ independentlyof each other are hydrogen, C₁-C₆ alkyl, C₁-C₆ halogenalkyl, C₃-C₆cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆ alkoxy, C₁-C₆halogenalkoxy, C₁-C₆ alkylthio or C₁-C₆halogenalkylthio; or R₁ and R₂ together are a C₂-C₅alkylene group, whichis unsubstituted or substituted by one or more C₁-C₆alkyl groups; may beprepared as described in reaction scheme 2.

Amino acid derivatives of formula XIV, in which R₁ and R₂ are as definedunder formula IIc, and R′ is C₁-C₆ alkyl, may be reduced into aminoalcohols of formula XIIc, in which R₁ and R₂ are as defined underformula IIc, by using known reduction methods. The amino alcohols offormula XIIc may be transformed into the desired compounds of formulaIIc via the phthalimide intermediates of formulae XIc, in which R₁ andR₂ are as defined under formula IIc, and Xc, in which B, R₁ and R₂ areas defined under formula IIc, by using the hydroxy derivatives offormula VI and applying the same methodology as described for scheme 1.

Intermediates of the formula II

in which B, R₁, R₂, R₃ and R₄ are as defined under formula I, may alsobe prepared as described in reaction scheme 3a.

Intermediates of formula XVI, in which B, R₁, R₂, R₃, and R₄ are asdefined under formula II, can be prepared by a Williamson reaction of ahydroxy derivative of formula VI, in which B is as defined under formulaII, with a 3-bromo-propan-1-ol derivative of formula XV, in which R₁,R₂, R₃, and R₄ are as defined under formula II, as described in, forexample, Journal Medicinal Chemistry, 46 (24), 5238-5248; 2003.

The compound of formula XVI can then be oxidized, for example by usingRuO₂/NaIO₄, into the corresponding propanoic acid derivative of formulaXVII, in which B, R₁, R₂, R₃, and R₄ are as defined under formula II.

The propanoic acid derivative of formula XVII can subsequently betransformed into a BOC-protected carbamate derivative of formula XVIII,in which B, R₁, R₂, R₃, and R₄ are as defined under formula II, viaCurtius rearrangement of its hydrazide derivative prepared by the use ofDPPA and quenching of the isocyanate derivative in the presence oft-Bu-OH (structures of the hydrazide and isocyanate derivatives notshown).

The removal of the BOC-protection group of the compounds of formulaXVIII to form the compounds of formula II can be effected in thepresence of a strong acid, such as HCl.

Alternatively, compounds of formula II (chiral if R₁ is different fromR₂) may also be prepared as described in reaction scheme 3b:

Chiral compounds of formula XXIVb, in which R₁, R₂, R₃, and R₄ are asdefined under formula Ib and R₁ is different from R₂, may be prepared byreacting an chiral amino alcohol of formula XXV, in which R₁, R₂, R₃,and R₄ are as defined under formula Ib and R₁ is different from R₂, withBoc₂O under standard conditions. Cyclic sulfamidites of formula XXIIIb,in which R₁, R₂, R₃, and R₄ are as defined under formula Ib, can then beprepared from the compounds of formula XXIVb by using SOCl₂. Thiscyclisation reaction may be performed in the presence of a base. Asuitable base is pyridine. Suitable solvents include dichloromethane andnitriles such as acetonitrile and propionitrile. The reactiontemperature typically lies in the range of −50° C. to 20° C.

Cyclic sulfamidates of formula XXIIb, in which A, R₁, R₂, R₃, and R₄ areas defined under formula Ib, may be prepared oxidation of the cyclicsulfamidites of formula XXIIIb. Suitable oxidation reagents are RuO₄ andRuCl₃.3H₂O in combination with NaIO₄. Suitable solvents include mixturesof nitriles and water; as nitrile can be used, for example, acetonitrileor propionitrile. The reaction temperature typically lies in the rangeof 0° C. to 30° C.

The cyclic sulfamidates of formula XXIIb may then react with compoundsof formula VI, in which B is as defined under formula Ib, to formcompounds of formula XVIII. This ring-opening by using oxygennucleophiles may be performed in the presence of a base. Suitable basesinclude carbonates, such as lithium hydroxide, cesium carbonate,potassium carbonate, or metal hydrides, such as sodium hydride andlithium hydride. Suitable solvents include N,N-dimethylformamide,dimethylacetamide and DMSO. The reaction temperature can vary withinwide limits, but typically is from ambient temperature to 100° C.

Intermediates of formula IId

in which B is as defined under formula I and R₃ and R₄ independently ofeach other are hydrogen, C₁-C₆ alkyl, C₁-C₆ halogenalkyl,C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆halogenalkoxy, C₁-C₆alkylthio or C₁-C₆halogenalkylthio or R₃ and R₄ together are a C₂-C₅alkylene group, whichis unsubstituted or substituted by one or more C₁-C₆alkyl groups; may beprepared as described in reaction scheme 4.

Nitriles of the formula XX, in which B, R₃ and R₄ are as defined underformula IId, can be prepared by reaction of a compound of formula XIX,in which R₃ and R₄ are as defined under formula IId, and Hal stands forhalogen, with a compound of formula VI, in which B is as defined underformula IId, by using known methods.

The nitrile of formula XX can then undergo a Ti-(II)-mediated couplingwith a Grignard-reagent of formula XXI, in which Hal stands for halogen,to afford the desired compounds of formula IId. Reaction conditions forthis reaction are described, for example, by P. Bertus and J. Szymoniak(J. Org. Chem., 2002, 67, 3965-3968) and in EP-1-595-873.

Compounds of formula Ib

in which A and B are as defined under formula I and R₁, R₂, R₃ and R₄independently of each other are hydrogen, C₁-C₆ alkyl, C₁-C₆halogenalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl,C₂-C₆alkynyl or C₂-C₆ haloalkynyl; or R₁ and R₂ together are aC₂-C₅alkylene group, which is unsubstituted or substituted by one ormore C₁-C₆alkyl groups; or R₁ and R₃ together are a C₂-C₅alkylene group,which is unsubstituted or substituted by one or more C₁-C₆alkyl groups;or R₃ and R₄ together are a C₂-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups; may be prepared asdescribed in reaction scheme 5.

Compounds of formula XXIV, in which A, R₁, R₂, R₃, and R₄ are as definedunder formula Ib, may be prepared by reacting an amino alcohol offormula XXV, in which R₁, R₂, R₃, and R₄ are as defined under formulaIb, with a compound of formula III, in which A is as defined underformula Ib and Hal stands for halogen, preferably chloro, in thepresence of a base, such as triethylamine, Hunig base, sodiumbicarbonate, sodium carbonate, potassium carbonate, pyridine orquinoline, but preferably triethylamine, and in a solvent, such asdiethylether, TBME, THF, dichloromethane, chloroform, DMF or NMP, forbetween 10 minutes and 48 hours, preferably 12 to 24 hours, and between0° C. and reflux, preferably 20 to 25° C.

Cyclic sulfamidites of formula XXIII, in which A, R₁, R₂, R₃, and R₄ areas defined under formula Ib, can then be prepared from the compounds offormula XXIV by using SOCl₂. This cyclisation reaction may be performedin the presence of a base. A suitable base is pyridine. Suitablesolvents include dichloromethane and nitriles such as acetonitrile andpropionitrile. The reaction temperature typically lies in the range of−50° C. to 20° C.

Cyclic sulfamidates of formula XXII, in which A, R₁, R₂, R₃, and R₄ areas defined under formula Ib, may be prepared oxidation of the cyclicsulfamidites of formula XXIII. Suitable oxidation reagents are RuO₄ andRuCl₃.3H₂O in combination with NaIO₄. Suitable solvents include mixturesof nitriles and water; as nitrile can be used, for example, acetonitrileor propionitrile. The reaction temperature typically lies in the rangeof 0° C. to 30° C.

For a review of preparation methods for cyclic sulfates andsulfamidates, see Lohray, B. B. in Advances in Heterocyclic Chemistry;Katritzky, A. R., Ed.; Academic Press: San Diego, 1997; Vol. 68, pp89-180; and Posakony J. J., J. Org. Chem., 2002, 67, 5164-5169.

The cyclic sulfamidates of formula XXII may then react with compounds offormula VI, in which B is as defined under formula Ib, to form compoundsof formula Ib. This ring-opening by using oxygen nucleophiles may beperformed in the presence of a base. Suitable bases include carbonates,such as lithium hydroxide, cesium carbonate, potassium carbonate, ormetal hydrides, such as sodium hydride and lithium hydride. Suitablesolvents include N,N-dimethylformamide, dimethylacetamide and DMSO. Thereaction temperature can vary within wide limits, but typically is fromambient temperature to 100° C.

Alternatively, compounds of formula Ib may be prepared by the reactionof compounds of formula XXIV and compounds of formula XXVI, in which Bis as defined under formula Ib and Hal stands for halogen. Thisnucleophilic substitution reaction may preferably be used in the casethat the compound of formula XXVI is an activated halogen-aromaticcompound. In the case that the compound of formula XXVI is anon-activated compound, said reaction may be carried out underpalladium- or copper-catalyst mediated conditions.

For the synthesis of 1.3-substituted naphthols see Annalen 1930, 484,245-300

For the synthesis of 5-hydroxybenzo[b]thiophene see: SyntheticCommunications, 1991, 21, 959-964.

The compounds of the formulae V, VI, VII, XII, XIV, XV, XIX, XXV andXXVI, wherein the substituents as described above, are known andcommercially available or can be prepared according to theabove-mentioned references or according to methods known in the art.

The compounds of the formula III and IIIb, wherein the substituents asdescribed above, are known and partially commercially available. Theycan be prepared analogously as described, for example, in WO 00/09482,WO 02/38542, WO 04/018438, EP-0-589-301, WO 93/11117 and Arch. Pharm.Res. 2000, 23 (4), 315-323.

For preparing all further compounds of the formula I functionalizedaccording to the definitions of A, B, R₁, R₂, R₃ and R₄, there are alarge number of suitable known standard methods, such as alkylation,halogenation, acylation, amidation, oximation, oxidation and reduction.The choice of the preparation methods which are suitable are dependingon the properties (reactivity) of the substituents in the intermediates.

The reactions to give compounds of the formula I are advantageouslycarried out in aprotic inert organic solvents. Such solvents arehydrocarbons such as benzene, toluene, xylene or cyclohexane,chlorinated hydrocarbons such as dichloromethane, trichloromethane,tetrachloromethane or chlorobenzene, ethers such as diethyl ether,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,tetrahydrofuran or dioxane, nitriles such as acetonitrile orpropionitrile, amides such as N,N-dimethylformamide, diethylformamide orN-methylpyrrolidinone. The reaction temperatures are advantageouslybetween −20° C. and +120° C. In general, the reactions are slightlyexothermic and, as a rule, they can be carried out at ambienttemperature. To shorten the reaction time, or else to start thereaction, the mixture may be heated briefly to the boiling point of thereaction mixture. The reaction times can also be shortened by adding afew drops of base as reaction catalyst. Suitable bases are, inparticular, tertiary amines such as trimethylamine, triethylamine,quinuclidine, 1,4-diazabicyclo[2.2.2]octane,1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo-[5.4.0]undec-7-ene.However, inorganic bases such as hydrides, e.g. sodium hydride orcalcium hydride, hydroxides, e.g. sodium hydroxide or potassiumhydroxide, carbonates such as sodium carbonate and potassium carbonate,or hydrogen carbonates such as potassium hydrogen carbonate and sodiumhydrogen carbonate may also be used as bases. The bases can be used assuch or else with catalytic amounts of a phase-transfer catalyst, forexample a crown ether, in particular 18-crown-6, or a tetraalkylammoniumsalt.

The compounds of formula I can be isolated in the customary manner byconcentrating and/or by evaporating the solvent and purified byrecrystallization or trituration of the solid residue in solvents inwhich they are not readily soluble, such as ethers, aromatichydrocarbons or chlorinated hydrocarbons.

The compounds I and, where appropriate, the tautomers thereof, can bepresent in the form of one of the isomers which are possible or as amixture of these, for example in the form of pure isomers, such asantipodes and/or diastereomers, or as isomer mixtures, such asenantiomer mixtures, for example racemates, diastereomer mixtures orracemate mixtures, depending on the number, absolute and relativeconfiguration of asymmetric carbon atoms which occur in the moleculeand/or depending on the configuration of non-aromatic double bonds whichoccur in the molecule; the invention relates to the pure isomers andalso to all isomer mixtures which are possible and is to be understoodin each case in this sense hereinabove and hereinbelow, even whenstereochemical details are not mentioned specifically in each case.

The compounds I and, where appropriate, the tautomers thereof, can, ifappropriate, also be obtained in the form of hydrates and/or includeother solvents, for example those which may have been used for thecrystallization of compounds which are present in solid form.

The intermediates of the formula II

in which B, R₁, R₂, R₃ and R₄ are as defined under formula I, are noveland were developed specifically for the preparation of the compounds ofthe formula I. Accordingly, these intermediates of the formula II alsoform part of the subject-matter of the present invention.

The intermediates of the formula IIa

in which B, R₁, R₂, R₃ and R₄ are as defined under formula I, and R₂₀ isC₃-C₇cycloalkyl preferably cyclopropyl, are novel and were developedspecifically for the preparation of the compounds of the formula I.Accordingly, these intermediates of the formula II also form part of thesubject-matter of the present invention.

The intermediates of the formula IV

in which B is as defined under formula I and R₁, R₃ and R₄ independentlyof each other are hydrogen, C₁-C₆ alkyl, C₁-C₆ halogenalkyl, C₃-C₆cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆ alkoxy, C₁-C₆ halogenalkoxy, C₁-C₆ alkylthio or C₁-C₆halogenalkylthio; or R₁ and R₃ together are a C₂-C₅alkylene group, whichis unsubstituted or substituted by one or more C₁-C₆alkyl groups; or R₃and R₄ together are a C₂-C₅alkylene group, which is unsubstituted orsubstituted by one or more C₁-C₆alkyl groups; are novel and weredeveloped specifically for the preparation of the compounds of theformula I.

Accordingly, these intermediates of the formula IV also form part of thesubject-matter of the present invention.

The intermediates of the formula XXIV

in which A is as defined under formula I and R₁, R₂, R₃ and R₄independently of each other are hydrogen, C₁-C₆ alkyl, C₁-C₆halogenalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl,C₂-C₆alkynyl or C₂-C₆ haloalkynyl; or R₁ and R₂ together are aC₂-C₅alkylene group, which is unsubstituted or substituted by one ormore C₁-C₆alkyl groups; or R₁ and R₃ together are a C₂-C₅alkylene group,which is unsubstituted or substituted by one or more C₁-C₆alkyl groups;or R₃ and R₄ together are a C₂-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups; are novel and weredeveloped specifically for the preparation of the compounds of theformula I. Accordingly, these intermediates of the formula XXIV alsoform part of the subject-matter of the present invention.

The intermediates of the formula XXIVa

in which A is as defined under formula I, R₂₀ is C₃-C₇cycloalkyl,preferably cyclopropyl, and R₁, R₂, R₃ and R₄ independently of eachother are hydrogen, C₁-C₆ alkyl, C₁-C₆ halogenalkyl, C₃-C₆ cycloalkyl,C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆alkynyl or C₂-C₆ haloalkynyl; orR₁ and R₂ together are a C₂-C₆alkylene group, which is unsubstituted orsubstituted by one or more C₁-C₆alkyl groups; or R₁ and R₃ together area C₂-C₆alkylene group, which is unsubstituted or substituted by one ormore C₁-C₆alkyl groups; or R₃ and R₄ together are a C₂-C₅alkylene group,which is unsubstituted or substituted by one or more C₁-C₆alkyl groups;are novel and were developed specifically for the preparation of thecompounds of the formula I. Accordingly, these intermediates of theformula XXIV also form part of the subject-matter of the presentinvention.

The intermediates of the formula XXIIB

in which A is as defined under formula I; X₁ is —S(O)— or —S(O)₂—; andR₁, R₂, R₃ and R₄ independently of each other are hydrogen, C₁-C₆ alkyl,C₁-C₆ halogenalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl,C₂-C₆alkynyl or C₂-C₆ haloalkynyl; or R₁ and R₂ together are aC₂-C₅alkylene group, which is unsubstituted or substituted by one ormore C₁-C₆alkyl groups; or R₁ and R₃ together are a C₂-C₅alkylene group,which is unsubstituted or substituted by one or more C₁-C₆alkyl groups;or R₃ and R₄ together are a C₂-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups; are novel and weredeveloped specifically for the preparation of the compounds of theformula I.

Accordingly, these intermediates of the formula XXIIB also form part ofthe subject-matter of the present invention.

It has now been found that the compounds of formula I according to theinvention have, for practical purposes, a very advantageous spectrum ofactivities for protecting useful plants against diseases that are causedby phytopathogenic microorganisms, such as fungi, bacteria or viruses.

The invention relates to a method of controlling or preventinginfestation of useful plants by phytopathogenic microorganisms, whereina compound of formula I is applied as active ingredient to the plants,to parts thereof or the locus thereof. The compounds of formula Iaccording to the invention are distinguished by excellent activity atlow rates of application, by being well tolerated by plants and by beingenvironmentally safe. They have very useful curative, preventive andsystemic properties and are used for protecting numerous useful plants.The compounds of formula I can be used to inhibit or destroy thediseases that occur on plants or parts of plants (fruit, blossoms,leaves, stems, tubers, roots) of different crops of useful plants, whileat the same time protecting also those parts of the plants that growlater e.g. from phytopathogenic microorganisms.

It is also possible to use compounds of formula I as dressing agents forthe treatment of plant propagation material, in particular of seeds(fruit, tubers, grains) and plant cuttings (e.g. rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil.

Furthermore the compounds of formula I according to the invention may beused for controlling fungi in related areas, for example in theprotection of technical materials, including wood and wood relatedtechnical products, in food storage or in hygiene management.

The compounds of formula I are, for example, effective against thephytopathogenic fungi of the following classes: Fungi imperfecti (e.g.Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercosporaand Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia,Puccinia). Additionally, they are also effective against the Ascomycetesclasses (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula)and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).Outstanding activity has been observed against powdery mildew (Erysiphespp.). Furthermore, the novel compounds of formula I are effectiveagainst phytopathogenic bacteria and viruses (e.g. against Xanthomonasspp, Pseudomonas spp, Erwinia amylovora as well as against the tobaccomosaic virus). Good activity has been observed against Asian soybeanrust (Phakopsora pachyrhizi).

Within the scope of the invention, useful plants to be protectedtypically comprise the following species of plants: cereal (wheat,barley, rye, oat, rice, maize, sorghum and related species); beet (sugarbeet and fodder beet); pomes, drupes and soft fruit (apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries andblackberries); leguminous plants (beans, lentils, peas, soybeans); oilplants (rape, mustard, poppy, olives, sunflowers, coconut, castor oilplants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers,melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges,lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae(avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee,eggplants, sugar cane, tea, pepper, vines, hops, bananas and naturalrubber plants, as well as ornamentals.

The term “useful plants” is to be understood as including also usefulplants that have been rendered tolerant to herbicides like bromoxynil orclasses of herbicides (such as, for example, HPPD inhibitors, ALSinhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron,EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising one or more selectivelyacting toxins, such as are known, for example, from toxin-producingbacteria, especially those of the genus Bacillus.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising antipathogenicsubstances having a selective action, such as, for example, theso-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392225). Examples of such antipathogenic substances and transgenic plantscapable of synthesising such antipathogenic substances are known, forexample, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. Themethods of producing such transgenic plants are generally known to theperson skilled in the art and are described, for example, in thepublications mentioned above.

The term “locus” of a useful plant as used herein is intended to embracethe place on which the useful plants are growing, where the plantpropagation materials of the useful plants are sown or where the plantpropagation materials of the useful plants will be placed into the soil.An example for such a locus is a field, on which crop plants aregrowing.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

The compounds of formula I can be used in unmodified form or,preferably, together with carriers and adjuvants conventionally employedin the art of formulation.

Therefore the invention also relates to compositions for controlling andprotecting against phytopathogenic microorganisms, comprising a compoundof formula I and an inert carrier, and to a method of controlling orpreventing infestation of useful plants by phytopathogenicmicroorganisms, wherein a composition, comprising a compound of formulaI as active ingredient and an inert carrier, is applied to the plants,to parts thereof or the locus thereof.

To this end compounds of formula I and inert carriers are convenientlyformulated in known manner to emulsifiable concentrates, coatablepastes, directly sprayable or dilutable solutions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations e.g. in polymeric substances. As with the type of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances. Thecompositions may also contain further adjuvants such as stabilizers,antifoams, viscosity regulators, binders or tackifiers as well asfertilizers, micronutrient donors or other formulations for obtainingspecial effects.

Suitable carriers and adjuvants can be solid or liquid and aresubstances useful in formulation technology, e.g. natural or regeneratedmineral substances, solvents, dispersants, wetting agents, tackifiers,thickeners, binders or fertilizers. Such carriers are for exampledescribed in WO 97/33890.

The compounds of formula I or compositions, comprising a compound offormula I as active ingredient and an inert carrier, can be applied tothe locus of the plant or plant to be treated, simultaneously or insuccession with further compounds. These further compounds can be e.g.fertilizers or micronutrient donors or other preparations whichinfluence the growth of plants. They can also be selective herbicides aswell as insecticides, fungicides, bactericides, nematicides,molluscicides or mixtures of several of these preparations, if desiredtogether with further carriers, surfactants or application promotingadjuvants customarily employed in the art of formulation.

A preferred method of applying a compound of formula I, or acomposition, comprising a compound of formula I as active ingredient andan inert carrier, is foliar application. The frequency of applicationand the rate of application will depend on the risk of infestation bythe corresponding pathogen. However, the compounds of formula I can alsopenetrate the plant through the roots via the soil (systemic action) bydrenching the locus of the plant with a liquid formulation, or byapplying the compounds in solid form to the soil, e.g. in granular form(soil application). In crops of water rice such granulates can beapplied to the flooded rice field. The compounds of formula I may alsobe applied to seeds (coating) by impregnating the seeds or tubers eitherwith a liquid formulation of the fungicide or coating them with a solidformulation.

A formulation, i.e. a composition comprising the compound of formula Iand, if desired, a solid or liquid adjuvant, is prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally,surface-active compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% byweight, preferably from 0.1 to 95% by weight, of the compound of formulaI, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid orliquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25%by weight, of a surfactant.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

Advantageous rates of application are normally from 5 g to 2 kg ofactive ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kga.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seeddrenching agent, convenient rates of application are from 10 mg to 1 gof active substance per kg of seeds. The rate of application for thedesired action can be determined by experiments. It depends for exampleon the type of action, the developmental stage of the useful plant, andon the application (location, timing, application method) and can, owingto these parameters, vary within wide limits.

Surprisingly, it has now been found that the compounds of formula I canalso be used in methods of protecting crops of useful plants againstattack by phytopathogenic organisms as well as the treatment of crops ofuseful plants infested by phytopathogenic organisms comprisingadministering a combination of glyphosate and at least one compound offormula I to the plant or locus thereof, wherein the plant is resistantor sensitive to glyphosate.

Said methods may provide unexpectedly improved control of diseasescompared to using the compounds of formula I in the absence ofglyphosate. Said methods may be effective at enhancing the control ofdisease by compounds of formula I. While the mixture of glyphosate andat least one compound of formula I may increase the disease spectrumcontrolled, at least in part, by the compound of formula I, an increasein the activity of the compound of formula I on disease species alreadyknown to be controlled to some degree by the compound of formula I canalso be the effect observed.

Said methods are particularly effective against the phytopathogenicorganisms of the kingdom Fungi, phylum Basidiomycot, classUredinomycetes, subclass Urediniomycetidae and the order Uredinales(commonly referred to as rusts). Species of rusts having a particularlylarge impact on agriculture include those of the family Phakopsoraceae,particularly those of the genus Phakopsora, for example Phakopsorapachyrhizi, which is also referred to as Asian soybean rust, and thoseof the family Pucciniaceae, particularly those of the genus Pucciniasuch as Puccinia graminis, also known as stem rust or black rust, whichis a problem disease in cereal crops and Puccinia recondita, also knownas brown rust.

An embodiment of said method is a method of protecting crops of usefulplants against attack by a phytopathogenic organism and/or the treatmentof crops of useful plants infested by a phytopathogenic organism, saidmethod comprising simultaneously applying glyphosate, including salts oresters thereof, and at least one compound of formula I, which hasactivity against the phytopathogenic organism to at least one memberselected from the group consisting of the plant, a part of the plant andthe locus of the plant.

The compounds of formula (I), or a pharmaceutical salt thereof,described above may also have an advantageous spectrum of activity forthe treatment and/or prevention of microbial infection in an animal.

“Animal” can be any animal, for example, insect, mammal, reptile, fish,amphibian, preferably mammal, most preferably human. “Treatment” meansthe use on an animal which has microbial infection in order to reduce orslow or stop the increase or spread of the infection, or to reduce theinfection or to cure the infection. “Prevention” means the use on ananimal which has no apparent signs of microbial infection in order toprevent any future infection, or to reduce or slow the increase orspread of any future infection.

According to the present invention there is provided the use of acompound of formula (I) in the manufacture of a medicament for use inthe treatment and/or prevention of microbial infection in an animal.There is also provided the use of a compound of formula (I) as apharmaceutical agent. There is also provided the use of a compound offormula (I) as an antimicrobial agent in the treatment of an animal.According to the present invention there is also provided apharmaceutical composition comprising as an active ingredient a compoundof formula (I), or a pharmaceutically acceptable salt thereof, and apharmaceutically acceptable diluent or carrier. This composition can beused for the treatment and/or prevention of antimicrobial infection inan animal. This pharmaceutical composition can be in a form suitable fororal administration, such as tablet, lozenges, hard capsules, aqueoussuspensions, oily suspensions, emulsions dispersible powders,dispersible granules, syrups and elixirs. Alternatively thispharmaceutical composition can be in a form suitable for topicalapplication, such as a spray, a cream or lotion. Alternatively thispharmaceutical composition can be in a form suitable for parenteraladministration, for example injection. Alternatively this pharmaceuticalcomposition can be in inhalable form, such as an aerosol spray.

The compounds of formula (I) may be effective against various microbialspecies able to cause a microbial infection in an animal. Examples ofsuch microbial species are those causing Aspergillosis such asAspergillus fumigatus, A. flavus, A. terrus, A. nidulans and A. niger,those causing Blastomycosis such as Blastomyces dermatitidis; thosecausing Candidiasis such as Candida albicans, C. glabrata, C.tropicalis, C. parapsilosis, C. krusei and C. lusitaniae; those causingCoccidioidomycosis such as Coccidioides immitis; those causingCryptococcosis such as Cryptococcus neoformans; those causingHistoplasmosis such as Histoplasma capsulatum and those causingZygomycosis such as Absidia corymbifera, Rhizomucor pusillus andRhizopus arrhizus. Further examples are Fusarium Spp such as Fusariumoxysporum and Fusarium solani and Scedosporium Spp such as Scedosporiumapiospermum and Scedosporium prolificans. Still further examples areMicrosporum Spp, Trichophyton Spp, Epidermophyton Spp, Mucor Spp,Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp,Paracoccidioides Spp and Histoplasma Spp.

The following non-limiting Examples illustrate the above-describedinvention in greater detail without limiting it.

PREPARATION EXAMPLES Example P1 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(4-acetyl-p-phenoxy)-1-methyl-ethyl]-amide (compound 1.098)

To a solution of 4-hydroxyacetophenone (0.14 g; 1 mmol) indimethylformamide (4 ml) sodium hydride 50% in oil (0.04 g; 1 mmol) isadded portion wise. The reaction mixture is stirred for 15 minutes atambient temperature followed by the addition of3-difluoromethyl-1-methyl-1H-pyrazol-4-yl)-4-methyl-2,2-dioxo-2-λ-*6*-[1,2,3]oxathiazolidin-3-yl)-methanone(0.33 g; 1.1 mmol), which is prepared as described in example P5c, indimethylformamide (0.5 ml). The reaction mixture is stirred for 1 h atambient temperature then poured onto 1M HCl (40 ml) and extracted withethyl acetate (2×30 ml). The combined ethyl acetate layers are washedwith water (20 ml) and then dried over Na₂SO₄. After removal of thesolvent the residue is purified by flash chromatography over silica gel(eluent: cyclo hexane/ethyl acetate 7:3). 0.16 g (46% of theory) of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(4-acetyl-p-phenoxy)-1-methyl-ethyl]-amide (compound 1.098) isobtained in form of a resin.

¹H NMR (400 MHz, CDCl₃): δ 1.40 (d, 3H, CH₃), 2.53 (s, 3H, CH₃), 3.90(s, 3H, CH₃), 4.05-4.12 (m, 2H, CH₂), 4.52-4.57 (m, 1H, CH), 6.68(m_(broad), 1H, NH), 6.71-6.98 (t, 1H, CHF₂), 6.94-6.97 (d, 2H, Ar—H),7.90-7.94 (m, 3H, 2H—Ar+1H, Pyrazol-H).

MS [M+H]⁺ 352.

Example P2 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(2,6-dimethyl-phenoxy)-1-methyl-ethyl]-amide (compound 1.166) and3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(4-bromo-2,6-dimethyl-phenoxy)-1-methyl-ethyl]-amide (compound 1.168)

At 0° C., a solution of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonylchloride (0.29 g; 1.5 mmol) in dichloromethane (3 ml) is added dropwiseto a stirred solution of 0.35 g (1.5 mmol) of a 4:1-mixture of2-(4-bromo-2,6-dimethyl-phenoxy)-1-methyl-ethylamine (compound Z1.168)and 2-(2,6-dimethyl-phenoxy)-1-methyl-ethylamine (compound Z1.166),which is prepared as described in example P6, and triethylamine (0.3 g;3 mmol) in dichloromethane (20 ml). The reaction mixture is stirred for1 h at ambient temperature and then allowed to stand for 2 h. Thereaction mixture is washed with 1M NaOH (10 ml) and 1M HCl (10 ml) andthen dried over Na₂SO₄. After removal of the solvent, 0.65 g of aresidue remained. Both reaction products are isolated bycolumn-chromatography (column from Waters, RP PrepC18, 10 μm, 50 mm×250mm; solvents: A=acetonitrile, B=water; gradient: 50% to 0% B in 15 min;flow rate: 2.0 ml/min):

a) 90 mg (18% of theory) of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(2,6-dimethyl-phenoxy)-1-methyl-ethyl]-amide (compound 1.166) isobtained in the form of a solid (m.p. 142-146° C.). Retention time forthis compound is 10.78 min.

¹H NMR (400 MHz, CDCl₃): δ 1.46-1.48 (d, 3H), 2.21 (2s, 6H), 3.77-3.87(ddd, 2H), 3.94 (s, 3H), 4.47-4.53 (m, 1H), 6.76-7.03 (t, 1H), 6.79 (s,1H), 6.91 (d, 1H), 7.00 (d, 2H), 7.93 (s, 1H).

MS [M+H]⁺ 338.

b) 390 mg (63% of theory) of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(4-bromo-2,6-dimethyl-phenoxy)-1-methyl-ethyl]-amide (compound 1.168)is obtained in the form of a solid (m.p. 119-121° C.). Retention timefor this compound is 12.53 min.

¹H NMR (400 MHz, CDCl₃): δ 1.44-1.46 (d, 3H), 2.21 (2s, 6H), 3.72-3.85(ddd, 2H), 3.89 (s, 3H), 4.46-4.51 (m, 1H), 6.76 (s, 1H), 6.77-7.03 (t,1H), 7.11 (s, 1H), 7.93 (s, 1H).

MS [M+H]⁺ 416/418.

Example P3 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[1-methyl-2-(2,4,6-tribromo-phenoxy)-ethyl]-amide (compound 1.193)

A mixture of 0.3 g (0.8 mmol)1-methyl-2-(2,4,6-tribromo-phenoxy)-ethylamine (compound Z1.193,prepared as described in example P7) and 0.15 g (0.9 mmol)3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid in 2 ml pyridineunder a nitrogen atmosphere is cooled to 0° C. Phosphorus oxychloride(0.08 ml, 0.9 mmol) is added dropwise and the reaction mixture isstirred at 80° C. for 12 h. The reaction mixture is diluted with waterand 3-times extracted with ethyl acetate. The combined ethyl acetatelayers are washed with 1.5 N HCl, saturated NaHCO₃, water and brine,dried over sodium sulphate and evaporated to dryness. The residue ispurified by column chromatography (using 60-120 mesh-silica gel inhexane; eluent: ethyl acetate) to yield 0.12 g3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[1-methyl-2-(2,4,6-tribromo-phenoxy)-ethyl]-amide (27% of theory) as ayellow solid.

¹H NMR (400 MHz, CDCl3): δ 1.48-1.50 (d, 3H), 3.93 (s, 3H, NCH3),4.02-4.12 (ddd, 2H, CH2), 4.50-4.55 (m, 1H), 6.67 (s, 1H, NH), 6.78-7.05(t, 1H, CHF2), 7.65 (s, 1H), 7.88 (S, 1H, pyrazole-H),

LCMS {ESI+mode}: 543.8/545.77/549.81

Example P4 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(3-chloro-5-trifluoromethyl-pyridin-2-yloxy)-1-methyl-ethyl]-amide(compound 1.239)

A solution of 2.3 g 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid (2-hydroxy-1-methyl-ethyl)-amide (10.0 mmol, prepared as describedin example P5a) and 2.6 g 2-bromo-3-chloro-5-trifluoromethyl-pyridine(10 mmol) in dimethylformamide (30 ml) is treated at ambient temperaturewith 2.8 g potassium carbonate (20 mmol). The resulting suspension isstirred at 100° C. for 3 hours, cooled to ambient temperature, pouredonto water (200 ml) and extracted with ethyl acetate (2×100 ml). Thecombined ethyl acetate layers are washed with water (20 ml) and driedover Na₂SO₄. After removal of the solvent the residue (4.2 g in the formof an oil) is purified by flash chromatography over silica gel (eluent:cyclohexane/ethyl acetate 3:7). 1.4 g (34% of theory) of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(3-chloro-5-trifluoromethyl-pyridin-2-yloxy)-1-methyl-ethyl]-amide(compound 1.239) is obtained in form of a solid (mp. 115-118° C.).

¹H NMR (400 MHz, CDCl₃): δ 1.39-1.41 (d, 3H, CH₃), 3.91 (s, 3H, CH₃),4.46-4.54 (m, 2H, CH₂), 4.60-4.66 (m, 1H, CH), 6.63 (s, 1H, NH),6.67-6.81 (t, 1H, CHF2), 7.85 (d, 1H, Py-H), 7.90 (s, 1H, pyrazol-H),8.30 (t, 1H, Py-H).

MS [M+H]⁺ 413/415.

Example P5 Preparation of3-difluoromethyl-1-methyl-1H-pyrazol-4-yl)-4-methyl-2,2-dioxo-2-λ-*6*-[1,2,3]oxathiazolidin-3-yl)-methanonea) Preparation of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid (2-hydroxy-1-methyl-ethyl)-amide

At 0° C., a solution of 38.9 g3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride (0.2 mol) in100 ml dichloromethane is added dropwise to a stirred solution of 15 galaninol (0.2 mol) and 25 g triethylamine (0.25 mol) in 400 mldichloromethane. The reaction mixture is stirred for 1 h at ambienttemperature and then allowed to stand for 3 h at ambient temperature.After removal of the solvent the residue is purified by flashchromatography over silica gel 400 g (eluent: ethyl acetate/methanol19:1). 42 g (90% of theory) of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(2-hydroxy-1-methyl-ethyl)-amide is obtained in form of a solid (mp.81-87° C.).

¹H NMR (400 MHz, CDCl₃): δ 1.23-1.26 (d, 3H), 2.97 (s, 1H₂OH), 3.57-3.73(ddd, 2H), 3.94 (s, 3H), 4.17-4.23 (m, 1H), 6.57 (s, 1H), 6.75-7.02 (t,1H), 7.90 (s, 1H).

MS [M+H]⁺ 234.

b) Preparation of3-difluoromethyl-1-methyl-1H-pyrazol-4-yl)-4-methyl-2-oxo-2-λ-*4*-[1,2,3]oxathiazolidin-3-yl)-methanone

A solution of 14.6 ml SOCl₂ (200 mmol) in 98 ml dry acetonitrile undernitrogen atmosphere is cooled to −40° C. and 18.6 g3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(2-hydroxy-1-methyl-ethyl)-amide (80 mmol) in 70 ml acetonitrile isadded dropwise. 32.2 ml dry pyridine is added slowly. The mixture isthen allowed to warm to ambient temperature and stirred for 1.5 h. Thesolvent volume is reduced to 100 ml, 200 ml ethylacetate is added andthe resulting precipate is filtered off. The filtrate is concentrated toan oil residue. Purification is achieved by filtration over 40 g silicagel with 400 ml ethylacetate to obtain 10.5 g (47% of theory) of3-difluoromethyl-1-methyl-1H-pyrazol-4-yl)-4-methyl-2-oxo-2-λ-*4*-[1,2,3]oxathiazolidin-3-yl)-methanonein form of a resin.

MS [M+H]⁺ 280.

c) Preparation of3-difluoromethyl-1-methyl-1H-pyrazol-4-yl)-4-methyl-2,2-dioxo-2-λ-*6*-[1,2,3]oxathiazolidin-3-yl)-methanone

To a solution of 0.73 g3-difluoromethyl-1-methyl-1H-pyrazol-4-yl)-4-methyl-2-oxo-2-λ-*4*-[1,2,3]oxathiazolidin-3-yl)-methanone(2.6 mmol) in 3.8 ml acetonitrile is added 0.85 mgruthenium(III)chloride hydrate and 820 mg sodium(meta)periodate (3.8mmol) at 0° C. 3.8 ml water is added dropwise. The reaction becameexothermic up to 8° C. while cooling. The resulting dark suspension isallowed to warm to ambient temperature and stirred for 2 h, poured onto40 ml water and extracted with ethylacetate (2×30 ml). The organic layeris dried over anhydrous sodium sulphate, filtered over 5 g silica geland the solvent is removed to obtain 0.63 g (82% of theory) of3-difluoromethyl-1-methyl-1H-pyrazol-4-yl)-4-methyl-2,2-dioxo-2-λ-*6*-[1,2,3]oxathiazolidin-3-yl)-methanonein form of a resin. The compound is used in example P1 without furtherpurification

¹H NMR (400 MHz, CDCl₃): δ 1.51-1.53 (d, 3H), 3.98 (s, 3H),4.30-4.34+4.77-4.81 (m, 2H), 4.91-4.99 (m, 1H), 6.85-7.12 (t, 1H), 8.18(s, 1H).

MS [M+H]⁺ 296.

Example P6 Preparation of 2-(2,6-dimethyl-phenoxy)-1-methyl-ethylamine(compound Z1.166) and2-(4-bromo-2,6-dimethyl-phenoxy)-1-methyl-ethylamine (compound Z1.168)

In a sulfonation flask 0.43 g mexiletine hydrochloride (CAS5370-01-4, 2mol) is added to 10 ml glacial acetic acid. The resulting solution iscooled to 10° C. 0.32 g bromine (2 mmol) is added dropwise. The reactionmixture is stirred for 14 h at ambient temperature and poured ontoice-water. The pH of the mixture is adjusted to 10 with 5M NaOH and themixture is extracted with ethyl acetate (2×30 ml). The combined ethylacetate layers are washed with brine, dried over MgSO₄, filtered anddried under reduced pressure. 0.42 g of a 1:4-mixture of2-(2,6-dimethyl-phenoxy)-1-methyl-ethylamine (compound Z1.166) and2-(4-bromo-2,6-dimethyl-phenoxy)-1-methyl-ethylamine (compound Z1.168)is obtained in the form of a brown oil. The mixture is used in exampleP2 without further purification.

Example P7 1-Methyl-2-(2,4,6-tribromo-phenoxy)-ethylamine (compoundZ1.193) a) Preparation of 1-(2,4,6-tribromo-phenoxy)-propan-2-one

A mixture of 5 g 2,4,6-tribromophenol (15 mmol), 1.4 g 1-chloroacetone(15 mmol), 4.16 g anhydrous potassium carbonate (30 mmol) and 20 ml DMFis stirred at 27° C. Completion of the reaction is confirmed by TLC. Thereaction mass is diluted with water and extracted with ethylacetate Theorganic layer is washed with water and brine, dried over anhydroussodium sulphate and concentrated to obtain 5.6 g1-(2,4,6-tribromo-phenoxy)-propan-2-one (97%).

¹H NMR (400 MHz, CDCl₃): −2.42 δ (s, 3H), 4.48 δ (s, 2H), 7.67 δ (s,1H).

b) Preparation of 1-methyl-2-(2,4,6-tribromo-phenoxy)-ethylamine(compound Z1.193)

To a solution of 1 g 1-(2,4,6-tribromo-phenoxy)-propan-2-one (2.6 mmol)in 20 ml methanol is added 2.9 g ammonium acetate (39 mmol). The mixtureis cooled to 0° C. and 0.81 g sodiumcyanoborohydride (13 mmol) is added.The reaction mixture is stirred overnight at ambient temperature. Thecompletion of the reaction is confirmed by TLC. The reaction mixture isconcentrated and the remaining residue is dissolved with 1.5 N HCl andwashed with diethylether. The aqueous layer is neutralised and extractedwith ethylacetate. The ethylacetate layer is dried over anhydrous sodiumsulphate and the solvent removed. 0.32 g1-methyl-2-(2,4,6-tribromo-phenoxy)-ethylamine (32%) is obtained.

LCMS—385.8/389.79/391.80

Example P8 Preparation of(S)-2-(2,6-dimethyl-phenoxy)-1-methyl-ethylamine hydrochloride (compoundZ1.166 (S-enantiomere)) a) Preparation of(S)-4-Methyl-2-oxo-2-λ-*4*-[1,2,3]oxathiazolidine-3-carboxylic acidtert-butyl ester

To a cooled (−50° C.) solution of SOCl₂ (53 ml, 77 mmol), imidazole(18.6 g, 274 mmol) and Et₃N (20.4 ml, 147 mmol) in anhydrous CH₂Cl₂ (550mL) is added dropwise, a solution of (S)—N-Boc alaminol (12.0 g, 68mmol) in anhydrous CH₂Cl₂ (150 mL) over 0.5 h. The mixture is thenwarmed to 0° C. and stirred for 4 h prior to the addition of water (600mL). The organic portion is isolated, washed with brine (600 mL), dried(Na₂SO₄) and concentrated in vacuo to afford intermediate cyclicsulfamidite (15.14 g, 100%) as a colourless oil. This material is usedimmediately in the next stage without further purification.

b) Preparation of(S)-4-2,2-dioxo-2-λ-*6*-[1,2,3]oxathiazolidine-3-carboxylic acidtert-butyl ester

To an ice-cooled (0° C.) solution of intermediate cyclic sulfamiditefrom step a (15.14 g, 68 mmol) in MeCN (540 mL) is added sequentiallyNaIO₄ (72.0 g, 337 mmol), RuCl₃*H₂O (13 mg) and then water (420 mL). Themixture is stirred at 0° C. for 2 h and then diluted with water (900 mL)and extracted with Et₂O (2×1100 mL). The organic extracts are combined,washed with water (1200 mL) and then brine (1200 mL), dried (Na₂SO₄) andconcentrated in vacuo. The residue is filtered through a pad of SiO₂(60, eluting with Et₂O) to afford cyclic sulfamidate 4 (12.6 g, 78%, 4:1rotamer ratio) as a colourless, crystalline solid; m.p. 112-120° C.(EtOAc-hexanes); [α]_(D25)+5.29 (c=5.4, CHCl₃); δ_(H) (400 MHz, CDCl₃)(data for major rotamer only) 1.50 (3H, d, J=6.5, C4-CH₃), 1.53 (9H, s,NCO₂C(CH₃)₃), 4.00-4.10 (1H, m, C4-H), 4.68 (1H, dd, J=9.5 and 9.0,C3-H), 4.79 (1H, dd, J=9.0 and 7.0, C3-H).

c) Preparation of (S)-2-(2,6-dimethyl-phenoxy)-1-methyl-ethylaminehydrochloride (compound Z1.166 (S-enantiomere))

To a solution of 2,6-dimethylphenol (122 mg, 1.01 mmol) in anhydrous DMF(11 ml) is added NaH (50% dispersion in mineral oil, 50 mg, 1.01 mmol)and the resulting mixture is stirred at ambient temperature for 10minutes. (S)-4-2,2-dioxo-2-λ-*6*-[1,2,3]oxathiazolidine-3-carboxylicacid tert-butyl ester (200 mg, 0.84 mmol) in anhydrous DMF (4 ml) isadded and the mixture is stirred at r.t. for 3 h prior to concentrationin vacuo. The residue is suspended in dioxane (6 ml), water (100 μL) andconc. H₂SO₄ (100 μL) are added and the mixture is stirred at ambienttemperature for 0.5 h. Further conc. H₂SO₄ (100 μL) is added and themixture is stirred at ambient temperature for another 0.5 h. The mixtureis neutralised with saturated aq. NaHCO₃ and extracted with CH₂Cl₂ (3×30mL). The combined organic extracts are concentrated in vacuo to affordcrude amine (200 mg), as a brownish oil. This crude material is solvedin diethylether (3 ml) and treated with 1 N HCl in diethylether to forma precipate. The solid is filtered of and dried in vacuo to afford (55mg; 37%) of pure (S)-2-(2,6-dimethyl-phenoxy)-1-methyl-ethylaminehydrochloride in form of a white solid (mp. 190-193° C.). [α]_(D24)+2.6(c=1.0, MeOH).

The compound Z1.166 (S-enantiomere) is further transformed into compound1.166 (S-enantiomere) by known methods.

Tables 1 to 7: Compounds of Formula IA

The invention is further illustrated by the preferred individualcompounds of formula (IA) listed below in Tables 1 to 7. Characterisingdata is given in Table 12.

whereinB is one of the preferred groups B1 to B26, B28 or B29:

Each of Tables 1 to 7, which follow the Table Y below, comprises 643compounds of the formula (IA) in which R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ and have the values given in Table Y and A has the value givenin the relevant Table 1 to 7. Thus Table 1 corresponds to Table Y when Yis 1 and A has the value given under the Table 1 heading, Table 2corresponds to Table Y when Y is 2 and A has the value given under theTable 2 heading, and so on for Tables 3 to 7.

In Tables 1 to 11 below “Me” stands for methyl, “Et” stands for ethyl,“i-Pr” stands for isopropyl, “c-Pr” stands for cyclopropyl and “t-Bu”stands for tertiary butyl.

TABLE Y Cpd No. R₂ R₁ R₃ B R₁₀ R₁₁ R₁₂ R₁₃ R₁₄ Y.001 H H H B1 Cl H H H HY.002 H H H B1 Cl Cl H H H Y.003 H H H B1 Cl H Cl H H Y.004 H H H B1 ClH H Cl H Y.005 H H H B1 Cl H H H Cl Y.006 H H H B1 H Cl Cl H H Y.007 H HH B1 H Cl H Cl H Y.008 H H H B1 Cl H Cl H Cl Y.009 H H H B1 Cl H Br H ClY.010 H H H B1 Cl H I H Cl Y.011 H H H B1 Cl H CHF₂ H Cl Y.012 H H H B1Cl H CF₃ H Cl Y.013 H H H B1 Cl H C≡C—H H Cl Y.014 H H H B1 Cl H C≡C-MeH Cl Y.015 H H H B1 Cl H C≡C—Si(Me)₃ H Cl Y.016 H H H B1 Cl H C≡C-t-Bu HCl Y.017 H H H B1 Cl H C≡C-i-Pr H Cl Y.018 H H H B1 Cl H C≡C—CH₂OMe H ClY.019 H H H B1 Cl H C≡C-p-Cl-phenyl H Cl Y.020 H H H B1 Cl H p-Cl-phenylH Cl Y.021 H H H B1 Cl H CHO H Cl Y.022 H H H B1 Cl H CH═NOMe H Cl Y.023H H H B1 Cl H COMe H Cl Y.024 H H H B1 Cl H C(Me)═NOMe H Cl Y.025 H H HB1 Cl H NO₂ H Cl Y.026 H H H B1 Cl H NH₂ H Cl Y.027 H H H B1 Cl H NHMe HCl Y.028 H H H B1 Cl H N(Me)₂ H Cl Y.029 H H H B1 Cl H NHCOMe H Cl Y.030H H H B1 Cl H N═CHNEt(Me) H Cl Y.031 H H H B1 Cl H OCF₃ H Cl Y.032 H H HB1 Cl H OCH₂CH═CHCl₂ H Cl Y.033 H H H B1 Cl H p-Cl-phenoxy H Cl Y.034 HH H B1 Cl Me Cl H Cl Y.035 H H H B1 Cl Cl Cl H Cl Y.036 H H H B1 Cl H ClCl Cl Y.037 H H H B1 Cl Cl Cl Cl Cl Y.038 H H H B1 Cl H H H Me Y.039 H HH B1 Cl H Cl H Me Y.040 H H H B1 Cl H Br H Me Y.041 H H H B1 Cl H CF₃ HMe Y.042 H H H B1 Cl H C≡C—H H Me Y.043 H H H B1 Cl H C≡C—CH₂OMe H MeY.044 H H H B1 Cl H C(Me)═NOMe H Me Y.045 H H H B1 Cl H H H CHO Y.046 HH H B1 Cl H Cl H CHO Y.047 H H H B1 Cl H Br H CHO Y.048 H H H B1 Cl HCF₃ H CHO Y.049 H H H B1 Cl H C≡C—H H CHO Y.050 H H H B1 Cl H C≡C—CH₂OMeH CHO Y.051 H H H B1 Cl H C(Me)═NOMe H CHO Y.052 H H H B1 Cl H H H OMeY.053 H H H B1 Cl H Cl H OMe Y.054 H H H B1 Cl H Br H OMe Y.055 H H H B1Cl H CF₃ H OMe Y.056 H H H B1 Cl H C≡C—H H OMe Y.057 H H H B1 Cl HC≡C—CH₂OMe H OMe Y.058 H H H B1 Cl H C(Me)═NOMe H OMe Y.059 H H H B1 OMeH H H OMe Y.060 H H H B1 OMe H Cl H OMe Y.061 H H H B1 OMe H Br H OMeY.062 H H H B1 OMe H CF₃ H OMe Y.063 H H H B1 OMe H C≡C—H H OMe Y.064 HH H B1 OMe H C≡C—CH₂OMe H OMe Y.065 H H H B1 OMe H C(Me)═NOMe H OMeY.066 H H H B1 Me H H H Me Y.067 H H H B1 Me H Cl H Me Y.068 H H H B1 MeH Br H Me Y.069 H H H B1 Me H I H Me Y.070 H H H B1 Me H CF₃ H Me Y.071H H H B1 Me H C≡C—H H Me Y.072 H H H B1 Me H Me H Me Y.073 H H H B1 Me HC≡C—CH₂OMe H Me Y.074 H H H B1 Me H C(Me)═NOMe H Me Y.075 H H H B1 Me HNO₂ H Me Y.076 H H H B1 Me H NH₂ H Me Y.077 H H H B1 Me H NHCOMe H MeY.078 H H H B1 Me H p-Cl-phenyl H Me Y.079 H H H B1 Me H H H CHO Y.080 HH H B1 Me H Cl H CHO Y.081 H H H B1 Me H Br H CHO Y.082 H H H B1 i-Pr HH H i-Pr Y.083 H H H B1 i-Pr H Cl H i-Pr Y.084 H H H B1 i-Pr H Br H i-PrY.085 H H H B1 t-Bu H H H t-Bu Y.086 H H H B1 t-Bu H Cl H t-Bu Y.087 H HH B1 t-Bu H Br H t-Bu Y.088 H H H B1 t-Bu H Me H t-Bu Y.089 H H H B1t-Bu H t-Bu H t-Bu Y.090 H H H B1 t-Bu H OMe H t-Bu Y.091 H H H B1 Br HH H Br Y.092 H H H B1 Br H Br H Br Y.093 H H H B1 F H H H F Y.094 H H HB1 F H Cl H F Y.095 H H H B1 F H Br H F Y.096 H H H B1 I H H H I Y.097 HH H B1 I H Cl H I Y.098 H Me H B1 H H COMe H H Y.099 H Me H B1 H F H F HY.100 H Me H B1 Me H Cl H H Y.101 H Me H B1 H Cl Cl H H Y.102 H Me H B1H t-Bu H t-Bu H Y.103 H Me H B1 Cl H Cl H H Y.104 H Me H B1 Cl H H Cl HY.105 H Me H B1 Cl H H H Cl Y.106 H Me H B1 H Cl Cl H H Y.107 H Me H B1H Cl H Cl H Y.108 H Me H B1 Cl H Cl H Cl Y.109 H Me H B1 Cl H Br H ClY.110 H Me H B1 Cl H I H Cl Y.111 H Me H B1 Cl H CHF₂ H Cl Y.112 H Me HB1 Cl H CF₃ H Cl Y.113 H Me H B1 Cl H C≡C—H H Cl Y.114 H Me H B1 Cl HC≡C-Me H Cl Y.115 H Me H B1 Cl H C≡C—Si(Me)₃ H Cl Y.116 H Me H B1 Cl HC≡C-t-Bu H Cl Y.117 H Me H B1 Cl H C≡C—C-i-Pr H Cl Y.118 H Me H B1 Cl HC≡C—CH₂OMe H Cl Y.119 H Me H B1 Cl H C≡C-p-Cl-phenyl H Cl Y.120 H Me HB1 Cl H p-Cl-phenyl H Cl Y.121 H Me H B1 Cl H CHO H Cl Y.122 H Me H B1Cl H CH═NOMe H Cl Y.123 H Me H B1 Cl H COMe H Cl Y.124 H Me H B1 Cl HC(Me)═NOMe H Cl Y.125 H Me H B1 Cl H NO₂ H Cl Y.126 H Me H B1 Cl H NH₂ HCl Y.127 H Me H B1 Cl H NHMe H Cl Y.128 H Me H B1 Cl H N(Me)₂ H Cl Y.129H Me H B1 Cl H NHCOMe H Cl Y.130 H Me H B1 Cl H N═CHNEt(Me) H Cl Y.131 HMe H B1 Cl H OCF₃ H Cl Y.132 H Me H B1 Cl H OCH₂CH═CHCl₂ H Cl Y.133 H MeH B1 Cl H p-Cl-phenoxy H Cl Y.134 H Me H B1 Cl Me Cl H Cl Y.135 H Me HB1 Cl Cl Cl H Cl Y.136 H Me H B1 Cl H Cl Cl Cl Y.137 H Me H B1 Cl Cl ClCl Cl Y.138 H Me H B1 Cl H H H Me Y.139 H Me H B1 Cl H Cl H Me Y.140 HMe H B1 Cl H Br H Me Y.141 H Me H B1 Cl H CF₃ H Me Y.142 H Me H B1 Cl HC≡C—H H Me Y.143 H Me H B1 Cl H C≡C—CH₂OMe H Me Y.144 H Me H B1 Cl HC(Me)═NOMe H Me Y.145 H Me H B1 Cl H H H CHO Y.146 H Me H B1 Cl H Cl HCHO Y.147 H Me H B1 Cl H Br H CHO Y.148 H Me H B1 Cl H CF₃ H CHO Y.149 HMe H B1 Cl H C≡C—H H CHO Y.150 H Me H B1 Cl H C≡C—CH₂OMe H CHO Y.151 HMe H B1 Cl H C(Me)═NOMe H CHO Y.152 H Me H B1 Cl H H H OMe Y.153 H Me HB1 Cl H Cl H OMe Y.154 H Me H B1 Cl H Br H OMe Y.155 H Me H B1 Cl H CF₃H OMe Y.156 H Me H B1 Cl H C≡C—H H OMe Y.157 H Me H B1 Cl H C≡C—CH₂OMe HOMe Y.158 H Me H B1 Cl H C(Me)═NOMe H OMe Y.159 H Me H B1 OMe H H H OMeY.160 H Me H B1 OMe H Cl H OMe Y.161 H Me H B1 OMe H Br H OMe Y.162 H MeH B1 OMe H CF₃ H OMe Y.163 H Me H B1 OMe H C≡C—H H OMe Y.164 H Me H B1OMe H C≡C—CH₂OMe H OMe Y.165 H Me H B1 OMe H C(Me)═NOMe H OMe Y.166 H MeH B1 Me H H H Me Y.167 H Me H B1 Me H Cl H Me Y.168 H Me H B1 Me H Br HMe Y.169 H Me H B1 Me H I H Me Y.170 H Me H B1 Me H CF₃ H Me Y.171 H MeH B1 Me H C≡C—H H Me Y.172 H Me H B1 Me H Me H Me Y.173 H Me H B1 Me HC≡C—CH₂OMe H Me Y.174 H Me H B1 Me H C(Me)═NOMe H Me Y.175 H Me H B1 MeH NO₂ H Me Y.176 H Me H B1 Me H NH₂ H Me Y.177 H Me H B1 Me H NHCOMe HMe Y.178 H Me H B1 Me H p-Cl-phenyl H Me Y.179 H Me H B1 Me H H H CHOY.180 H Me H B1 Me H Cl H CHO Y.181 H Me H B1 Me H Br H CHO Y.182 H Me HB1 i-Pr H H H i-Pr Y.183 H Me H B1 i-Pr H Cl H i-Pr Y.184 H Me H B1 i-PrH Br H i-Pr Y.185 H Me H B1 t-Bu H H H t-Bu Y.186 H Me H B1 t-Bu H Cl Ht-Bu Y.187 H Me H B1 t-Bu H Me H t-Bu Y.188 H Me H B1 t-Bu H t-Bu H t-BuY.189 H Me H B1 t-Bu H p-Cl-phenyl H t-Bu Y.190 H Me H B1 H H CF₃ H HY.191 H Me H B1 H H Br H H Y.192 H Me H B1 Br H H H Br Y.193 H Me H B1Br H Br H Br Y.194 H Me H B1 F H H H F Y.195 H Me H B1 F H Cl H F Y.196H Me H B1 F H Br H F Y.197 H Me H B1 I H H H I Y.198 H Me H B1 I H Cl HI Y.199 H Me H B1 I H Br H I Y.200 H Me H B1 I H I H I Y.201 H Me Me B1Cl H H H Cl Y.202 H Me Me B1 Cl H Cl H Cl Y.203 H Me Me B1 Br H H H BrY.204 H Me Me B1 Br H Br H Br Y.205 H Me Me B1 Me H H H Me Y.206 H Me MeB1 Me H Cl H Me Y.207 H Me Me B1 Me H Br H Me Y.208 H Me H B1 Cl H H HCl Y.209 Me Me H B1 Cl H Cl H Cl Y.210 Me Me H B1 Br H H H Br Y.211 MeMe H B1 Br H Br H Br Y.212 Me Me H B1 Me H Cl H Me Y.213 Me Me H B1 Me HBr H Me Y.214 i-Pr Me H B1 Me H H H Me Y.215 c-Pr Me H B1 Me H H H MeY.216 Et Et H B1 Me H H H Me Y.217 Et Et H B1 Me H Br H Me Y.218 CH₂CH₂H B1 Cl H H H H Y.219 CH₂CH₂ H B1 Me H H H Me Y.220 CH₂CH₂ H B1 Me H BrH Me Y.221 CH₂CH₂ H B1 H H Cl H H Y.222 CH₂CH₂ H B1 Cl H Cl H H Y.223CH₂CH₂ H B1 Cl H H H Cl Y.224 CH₂CH₂ H B1 Cl H Cl H Cl Y.225 CH₂CH₂ H B1Br H H H Br Y.226 CH₂CH₂ H B1 Br H Br H Br Y.227 H CH₂ B1 Me H H H MeY.228 H CH₂ B1 Me H Br H Me Y.229 H CH₂ B1 H H Cl H H Y.230 H CH₂ B1 ClH Cl H H Y.231 H CH₂ B1 Cl H H H Cl Y.232 H CH₂ B1 Cl H Cl H Cl Y.233 HCH₂ B1 Br H H H Br Y.234 H CH₂ B1 Br H Br H Br Y.235 H H H B2 Cl H Cl H— Y.236 H H H B2 Cl H Br H — Y.237 H H H B2 Br H Br H — Y.238 H H H B2Cl H CF₃ H — Y.239 H Me H B2 Cl H CF₃ H — Y.240 H Et H B2 Cl H CF₃ H —Y.241 Me Me H B2 Cl H CF₃ H — Y.242 H H Me B2 Cl H CF₃ H — Y.243 H Et HB2 Cl H CF₃ H — Y.244 CH₂CH₂ H B2 Cl H CF₃ H — Y.245 H CH₂ B2 Cl H CF₃ H— Y.246 H H H B3 Cl H H Cl — Y.247 H H H B3 Cl H H Br — Y.248 H H H B3Cl H H I — Y.249 H H H B3 Cl H H Me — Y.250 H H H B3 Me H H Cl — Y.251 HH H B3 Me H H Br — Y.252 H H H B3 Me H H Me — Y.253 H Me H B3 Cl H H Cl— Y.254 H Me H B3 Me H H Cl — Y.255 H H H B4 Cl H H Cl — Y.256 H H H B4Br H H Br — Y.247 H H H B4 Me H H Me — Y.258 H Me H B4 Cl H H Cl — Y.259H Me H B4 Br H H Br — Y.260 H Me H B4 Me H H Me — Y.261 H H H B5 Me H Me— — Y.262 H H H B5 Me H Me — — Y.263 H H H B5 H Me H — — Y.264 H H H B5H Cl H — — Y.265 H H H B5 H Br H — — Y.266 H H H B5 H CF₃ H — — Y.267 HMe H B5 Me H Me — — Y.268 H Me H B5 Me H Me — — Y.269 H Me H B5 H Me H —— Y.270 H Me H B5 H Cl H — — Y.271 H Me H B5 H Br H — — Y.272 H Me H B5H CF₃ H — — Y.273 H H H B6 Cl H Cl — — Y.274 H H H B6 Cl Cl Cl — — Y.275H H H B6 Cl Me Cl — — Y.276 H Me H B6 Cl H Cl — — Y.277 H Me H B6 Cl ClCl — — Y.278 H Me H B6 Cl Me Cl — — Y.279 H H H B7 Cl H — — — Y.280 H HH B7 Cl Cl — — — Y.281 H H H B7 Me Me — — — Y.282 H H H B7 OMe Me — — —Y.283 H H H B7 OMe Cl — — — Y.284 H H H B7 NHMe Cl — — — Y.285 H Me H B7Cl H — — — Y.286 H Me H B7 Cl Cl — — — Y.287 H Me H B7 Me Me — — — Y.288H Me H B7 OMe Me — — — Y.289 H Me H B7 OMe Cl — — — Y.290 H Me H B7 NHMeCl — — — Y.291 H H H B8 Cl H H — — Y.292 H H H B8 Cl Cl H — — Y.293 H HH B8 Cl Cl Cl — — Y.294 H H H B8 Cl H Cl — — Y.295 H H H B8 Me H H — —Y.296 H H H B8 Me Cl H — — Y.297 H H H B8 Me Cl Cl — — Y.298 H H H B8 MeMe H — — Y.299 H H H B8 Me H Me — — Y.300 H H H B8 Me Me Cl — — Y.301 HH H B8 Me Me Me — — Y.302 H Me H B8 Cl H H — — Y.303 H Me H B8 Cl Cl H —— Y.304 H Me H B8 Cl Cl Cl — — Y.305 H Me H B8 Cl H Cl — — Y.306 H Me HB8 Me H H — — Y.307 H Me H B8 Me Cl H — — Y.308 H Me H B8 Me Cl Cl — —Y.309 H Me H B8 Me Me H — — Y.310 H Me H B8 Me H Me — — Y.311 H Me H B8Me Me Cl — — Y.312 H Me H B8 Me Me Me — — Y.313 H H H B9 Cl Cl H — —Y.314 H H H B9 Cl Cl H — — Y.315 H H H B9 Cl Cl Cl — — Y.316 H H H B9 ClMe H — — Y.317 H H H B9 Cl Me Cl — — Y.318 H H H B9 Cl Me Me — — Y.319 HH H B9 Cl Cl Me — — Y.320 H H H B9 Me Cl H — — Y.321 H H H B9 Me Cl Cl —— Y.322 H H H B9 Me Cl Me — — Y.323 H H H B9 Me Me H — — Y.324 H H H B9Me Me Cl — — Y.325 H H H B9 Me Me Me — — Y.326 H Me H B9 Cl Cl H — —Y.327 H Me H B9 Cl Cl Cl — — Y.328 H Me H B9 Cl Me H — — Y.329 H Me H B9Cl Me Cl — — Y.330 H Me H B9 Cl Me Me — — Y.331 H Me H B9 Cl Cl Me — —Y.332 H Me H B9 Me Cl H — — Y.333 H Me H B9 Me Cl Cl — — Y.334 H Me H B9Me Cl Me — — Y.335 H Me H B9 Me Me H — — Y.336 H Me H B9 Me Me Cl — —Y.337 H Me H B9 Me Me Me — — Y.338 H H H B10 Cl H H — — Y.339 H H B B10Cl Cl H — — Y.340 H H H B10 Cl Cl Cl — — Y.341 H H H B10 Cl H Cl — —Y.342 H H H B10 Me H H — — Y.343 H H H B10 Me Cl H — — Y.344 H H H B10Me Cl Cl — — Y.345 H H H B10 Me Me H — — Y.346 H H H B10 Me H Me — —Y.347 H H H B10 Me Me Cl — — Y.348 H H H B10 Me Me Me — — Y.349 H Me HB10 Cl H H — — Y.350 H Me H B10 Cl Cl H — — Y.351 H Me H B10 Cl Cl Cl —— Y.352 H Me H B10 Cl H Cl — — Y.353 H Me H B10 Me H H — — Y.354 H Me HB10 Me Cl H — — Y.355 H Me H B10 Me Cl Cl — — Y.356 H Me H B10 Me Me H —— Y.347 H Me H B10 Me H Me — — Y.358 H Me H B10 Me Me Cl — — Y.359 H MeH B10 Me Me Me — — Y.360 H H H B11 Cl Cl H — — Y.361 H H H B11 Cl Cl H —— Y.362 H H H B11 Cl Cl Cl — — Y.363 H H H B11 Cl Me H — — Y.364 H H HB11 Cl Me Cl — — Y.365 H H H B11 Cl Me Me — — Y.366 H H H B11 Cl Cl Me —— Y.367 H H H B11 Me Cl H — — Y.368 H H H B11 Me Cl Cl — — Y.369 H H HB11 Me Cl Me — — Y.370 H H H B11 Me Me H — — Y.371 H H H B11 Me Me Cl —— Y.372 H H H B11 Me Me Me — — Y.373 H Me H B11 Cl Cl H — — Y.374 H Me HB11 Cl Cl Cl — — Y.375 H Me H B11 Cl Me H — — Y.376 H Me H B11 Cl Me Cl— — Y.377 H Me H B11 Cl Me Me — — Y.378 H Me H B11 Cl Cl Me — — Y.379 HMe H B11 Me Cl H — — Y.380 H Me H B11 Me Cl Cl — — Y.381 H Me H B11 MeCl Me — — Y.382 H Me H B11 Me Me H — — Y.383 H Me H B11 Me Me Cl — —Y.384 H Me H B11 Me Me Me — — Y.385 H H H B12 Cl H H — — Y.386 H H H B12Cl Cl H — — Y.387 H H H B12 Cl Cl Cl — — Y.388 H H H B12 Cl H Cl — —Y.389 H H H B12 Me H H — — Y.390 H H H B12 Me Cl H — — Y.391 H H H B12Me Cl Cl — — Y.392 H H H B12 Me Me H — — Y.393 H H H B12 Me H Me — —Y.394 H H H B12 Me Me Cl — — Y.395 H H H B12 Me Me Me — — Y.396 H Me HB12 Cl H H — — Y.397 H Me H B12 Cl Cl H — — Y.398 H Me H B12 Cl Cl Cl —— Y.399 H Me H B12 Cl H Cl — — Y.400 H Me H B12 Me H H — — Y.401 H Me HB12 Me Cl H — — Y.402 H Me H B12 Me Cl Cl — — Y.403 H Me H B12 Me Me H —— Y.404 H Me H B12 Me H Me — — Y.405 H Me H B12 Me Me Cl — — Y.406 H MeH B12 Me Me Me — — Y.407 H H H B13 Cl Cl H — — Y.408 H H H B13 Cl Cl H —— Y.409 H H H B13 Cl Cl Cl — — Y.410 H H H B13 Cl Me H — — Y.411 H H HB13 Cl Me Cl — — Y.412 H H H B13 Cl Me Me — — Y.413 H H H B13 Cl Cl Me —— Y.414 H H H B13 Me Cl H — — Y.415 H H H B13 Me Cl Cl — — Y.416 H H HB13 Me Cl Me — — Y.417 H H H B13 Me Me H — — Y.418 H H H B13 Me Me Cl —— Y.419 H H H B13 Me Me Me — — Y.420 H Me H B13 Cl Cl H — — Y.421 H Me HB13 Cl Cl Cl — — Y.422 H Me H B13 Cl Me H — — Y.423 H Me H B13 Cl Me Cl— — Y.424 H Me H B13 Cl Me Me — — Y.425 H Me H B13 Cl Cl Me — — Y.426 HMe H B13 Me Cl H — — Y.427 H Me H B13 Me Cl Cl — — Y.428 H Me H B13 MeCl Me — — Y.429 H Me H B13 Me Me H — — Y.430 H Me H B13 Me Me Cl — —Y.431 H Me H B13 Me Me Me — — Y.432 H H H B14 Cl H — — — Y.433 H H H B14Cl Me — — — Y.434 H H H B14 Br H — — — Y.435 H H H B14 Br Me — — — Y.436H H H B14 Me H — — — Y.437 H H H B14 Me Me — — — Y.438 H H H B14 CF₃ H —— — Y.439 H H H B14 CF₃ Me — — — Y.440 H H H B14 OMe H — — — Y.441 H H HB14 OMe Me — — — Y.442 H Me H B14 Cl H — — — Y.443 H Me H B14 Cl Me — —— Y.444 H Me H B14 Br H — — — Y.445 H Me H B14 Br Me — — — Y.446 H Me HB14 Me H — — — Y.447 H Me H B14 Me Me — — — Y.448 H Me H B14 CF₃ H — — —Y.449 H Me H B14 CF₃ Me — — — Y.450 H Me H B14 OMe H — — — Y.451 H Me HB14 OMe Me — — — Y.452 H H H B15 Cl Cl — — — Y.453 H H H B15 Me Me — — —Y.454 H H H B15 Br Br — — — Y.455 H H H B15 CF₃ CF₃ — — — Y.456 H H HB15 OMe Cl — — — Y.457 H Me H B15 Cl Cl — — — Y.458 H Me H B15 Me Me — —— Y.459 H Me H B15 Br Br — — — Y.460 H Me H B15 CF₃ CF₃ — — — Y.461 H MeH B15 OMe Cl — — — Y.462 H H H B16 Cl H — — — Y.463 H H H B16 Cl Cl — —— Y.464 H H H B16 Br H — — — Y.465 H H H B16 Br Br — — — Y.466 H H H B16Me H — — — Y.467 H H H B16 Me Me — — — Y.468 H H H B16 CF₃ H — — — Y.469H H H B16 CF₃ CF₃ — — — Y.470 H Me H B16 Cl H — — — Y.471 H Me H B16 ClCl — — — Y.472 H Me H B16 Br H — — — Y.473 H Me H B16 Br Br — — — Y.474H Me H B16 Me H — — — Y.475 H Me H B16 Me Me — — — Y.476 H Me H B16 CF₃H — — — Y.477 H Me H B16 CF₃ CF₃ — — — Y.478 H H H B17 Cl — — — — Y.479H H H B17 Br — — — — Y.480 H H H B17 Me — — — — Y.481 H H H B17 CF₃ — —— — Y.482 H Me H B17 Cl — — — — Y.483 H Me H B17 Br — — — — Y.484 H Me HB17 Me — — — — Y.485 H Me H B17 CF₃ — — — — Y.486 H H H B18 Cl H — — —Y.487 H H H B18 Br H — — — Y.488 H H H B18 Me H — — — Y.489 H H H B18CF₃ H — — — Y.490 H H H B18 Cl Me — — — Y.491 H H H B18 Br Me — — —Y.492 H H H B18 Me Me — — — Y.493 H H H B18 CF₃ Me — — — Y.494 H Me HB18 Cl H — — — Y.495 H Me H B18 Br H — — — Y.496 H Me H B18 Me H — — —Y.497 H Me H B18 CF₃ H — — — Y.498 H Me H B18 Cl Me — — — Y.499 H Me HB18 Br Me — — — Y.500 H Me H B18 Me Me — — — Y.501 H Me H B18 CF₃ Me — —— Y.502 H H H B19 Cl H — — — Y.503 H H H B19 Br H — — — Y.504 H H H B19Me H — — — Y.505 H H H B19 CF₃ H — — — Y.506 H H H B19 Cl Me — — — Y.507H H H B19 Br Me — — — Y.508 H H H B19 Me Me — — — Y.509 H H H B19 CF₃ Me— — — Y.510 H Me H B19 Cl H — — — Y.511 H Me H B19 Br H — — — Y.512 H MeH B19 Me H — — — Y.513 H Me H B19 CF₃ H — — — Y.514 H Me H B19 Cl Me — —— Y.515 H Me H B19 Br Me — — — Y.516 H Me H B19 Me Me — — — Y.517 H Me HB19 CF₃ Me — — — Y.518 H H H B20 Cl H H H H Y.519 H H H B20 Cl H Cl H HY.520 H H H B20 Br H H H H Y.521 H H H B20 Br H Br H H Y.522 H H H B20Me H H H H Y.523 H H H B20 CF₃ H H H H Y.524 H H H B20 COMe H H H HY.525 H H H B20 Cl H H Cl H Y.526 H Me H B20 Cl H H H H Y.527 H Me H B20Cl H Cl H H Y.528 H Me H B20 Br H H H H Y.529 H Me H B20 Br H Br H HY.530 H Me H B20 Me H H H H Y.531 H Me H B20 CF₃ H H H H Y.532 H Me HB20 COMe H H H H Y.533 H Me H B20 Cl H H Cl H Y.534 H H H B21 Cl H H H HY.535 H H H B21 H Cl H H H Y.536 H H H B21 Cl Cl H H H Y.537 H H H B21 HH H Cl H Y.538 H H H B21 Cl H H Cl H Y.539 H H H B21 H Cl H Cl H Y.540 HH H B21 Cl Cl H Cl H Y.541 H H H B21 Br H H H H Y.542 H H H B21 CF₃ H HH H Y.543 H H H B21 Me H H H H Y.544 H H H B21 Cl H H H H Y.545 H H HB21 Br H H Cl H Y.546 H H H B21 CF₃ H H Cl H Y.547 H H H B21 Me H H Cl HY.548 H H H B21 Cl H H Cl H Y.549 H Me H B21 Cl H H H H Y.550 H Me H B21H Cl H H H Y.551 H Me H B21 Cl Cl H H H Y.552 H Me H B21 H H H Cl HY.553 H Me H B21 Cl H H Cl H Y.554 H Me H B21 H Cl H Cl H Y.555 H Me HB21 Cl Cl H Cl H Y.556 H Me H B21 Br H H H H Y.557 H Me H B21 CF₃ H H HH Y.558 H Me H B21 Me H H H H Y.559 H Me H B21 Cl H H H H Y.560 H Me HB21 Br H H Cl H Y.561 H Me H B21 CF₃ H H Cl H Y.562 H Me H B21 Me H H ClH Y.563 H Me H B21 Cl H H Cl H Y.564 H Me H B21 Cl Cl H Br H Y.565 H MeH B21 Br Br H H H Y.566 H Me H B21 Br Br H Br H Y.567 H Me H B21 Me Me HH H Y.568 H Me H B21 Me Me H Cl H Y.569 H Me H B21 Me Me H Br H Y.570 HH H B22 Me H H H H Y.571 H H H B22 H H H H Cl Y.572 H H H B22 Me H H HCl Y.573 H H H B22 H H H Cl Cl Y.574 H H H B22 H H H NO₂ Cl Y.575 H H HB22 H H H Me Cl Y.576 H H H B22 H H H H Br Y.577 H H H B22 H H H Cl BrY.578 H H H B22 H H H Me Br Y.579 H H H B22 H H H Br Br Y.580 H Me H B22Me H H H H Y.581 H Me H B22 H H H H Cl Y.582 H Me H B22 Me H H H ClY.583 H Me H B22 H H H Cl Cl Y.584 H Me H B22 H H H NO₂ Cl Y.585 H Me HB22 H H H Me Cl Y.586 H Me H B22 H H H H Br Y.587 H Me H B22 H H H Cl BrY.588 H Me H B22 H H H Me Br Y.589 H Me H B22 H H H Br Br Y.590 H H HB23 Cl H H H H Y.591 H H H B23 Cl Cl H H H Y.592 H H H B23 Cl Me H H HY.593 H H H B23 Me H H H H Y.594 H H H B23 Me Cl H H H Y.595 H H H B23Me Me H H H Y.596 H H H B23 H H H H Me Y.597 H H H B23 Cl H H H Me Y.598H H H B23 Me H H H Me Y.599 H Me H B23 Cl H H H H Y.600 H Me H B23 Cl ClH H H Y.601 H Me H B23 Cl Me H H H Y.602 H Me H B23 Me H H H H Y.603 HMe H B23 Me Cl H H H Y.604 H Me H B23 Me Me H H H Y.605 H Me H B23 H H HH Me Y.606 H Me H B23 Cl H H H Me Y.607 H Me H B23 Me H H H Me Y.608 H HH B24 Cl H H H H Y.609 H H H B24 Br H H H H Y.610 H H H B24 CN H H H HY.611 H H H B24 Me H H H H Y.612 H H H B24 OMe H H H H Y.613 H H H B24Cl H Cl H H Y.614 H H H B24 Br H Cl H H Y.615 H H H B24 CN H Cl H HY.616 H H H B24 Me H Cl H H Y.617 H H H B24 OMe H Cl H H Y.618 H H H B24Cl H F H H Y.619 H H H B24 Br H F H H Y.620 H H H B24 CN H F H H Y.621 HH H B24 Me H F H H Y.622 H H H B24 OMe H F H H Y.623 H H H B24 Cl H H HF Y.624 H Me H B24 Cl H H H H Y.625 H Me H B24 Br H H H H Y.626 H Me HB24 CN H H H H Y.627 H Me H B24 Me H H H H Y.628 H Me H B24 OMe H H H HY.629 H Me H B24 Cl H Cl H H Y.630 H Me H B24 Br H Cl H H Y.631 H Me HB24 CN H Cl H H Y.632 H Me H B24 Me H Cl H H Y.633 H Me H B24 OMe H Cl HH Y.634 H Me H B24 Cl H F H H Y.635 H Me H B24 Br H F H H Y.636 H Me HB24 CN H F H H Y.637 H Me H B24 Me H F H H Y.638 H Me H B24 OMe H F H HY.639 H Me H B24 Cl H H H F Y.640 H Me H B25 Me H H H H Y.641 H Me H B25Cl H H H H Y.642 H Me H B25 OMe H H H H Y.643 H Me H B26 Me H H H HY.644 H Me H B26 Cl H H H H Y.645 H Me H B26 OMe H H H H Y.646 H Me HB28 H H Me Me H Y.647 H Me H B28 Me Me Me Me H Y.648 H Me H B28 H H ClCl H Y.649 H Me H B28 H H Br Br H Y.650 H Me H B28 H H Cl Br H Y.651 HMe H B28 H H Cl H H Y.652 H Me H B29 H H H Me Me Y.653 H Me H B29 Me MeH Me Me

Table 1 provides 653 compounds of formula (IA), wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y. For example, compound 1.001 has the followingstructure:

Table 2 provides 653 compounds of formula (IA) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 3 provides 653 compounds of formula (IA) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 4 provides 653 compounds of formula (IA) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 5 provides 653 compounds of formula (IA) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 6 provides 653 compounds of formula (IA) wherein A is

wherein the broken lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 7 provides 653 compounds of formula (IA) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Tables 1a to 7a: Compounds of Formula IB

The invention is further illustrated by the preferred individualcompounds of formula (IB) listed below in Tables 1a to 7a.

whereinB is one of the preferred groups B1 to B26, B28 or B29:

Each of Tables 1a to 7a, which follow the Table Y above, comprises 653compounds of the formula (IB) in which R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ and have the values given in Table Y and A has the value givenin the relevant Table 1a to 7a. Thus Table 1a corresponds to Table Ywhen Y is 1a and A has the value given under the Table 1a heading, Table2a corresponds to Table Y when Y is 2a and A has the value given underthe Table 2a heading, and so on for Tables 3a to 7a.

Table 1a provides 653 compounds of formula (IB), wherein A is

wherein the broken lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y. For example, compound 1a.001 has the followingstructure:

Table 2a provides 653 compounds of formula (IB) wherein A is

wherein the broken lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 3a provides 653 compounds of formula (IB) wherein A is

wherein the broken lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 4a provides 653 compounds of formula (IB) wherein A is

wherein the broken lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 5a provides 653 compounds of formula (IB) wherein A is

wherein the broken lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 6a provides 653 compounds of formula (IB) wherein A is

wherein the broken lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 7a provides 653 compounds of formula (IB) wherein A is

wherein the broken lines indicate the point of attachment of the group Ato the amide group, and R₁, R₂, R₃, B, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are asdefined in Table Y.

Table 8: Compounds of Formula IIA

The invention is further illustrated by the preferred individualcompounds of formula (IIA)

wherein B is one of the preferred groups B1 to B5 or B20 to B26, B28 orB29

The compound of formula (IIA) are listed below in Table 8.Characterising data is given in Table 12.

TABLE 8 Cpd No. R₂ R₁ R₃ B R₁₀ R₁₁ R₁₂ R₁₃ R₁₄ Z1.001 H H H B1 Cl H H HH Z1.002 H H H B1 Cl Cl H H H Z1.003 H H H B1 Cl H Cl H H Z1.004 H H HB1 Cl H H Cl H Z1.005 H H H B1 Cl H H H Cl Z1.006 H H H B1 H Cl Cl H HZ1.007 H H H B1 H Cl H Cl H Z1.008 H H H B1 Cl H Cl H Cl Z1.009 H H H B1Cl H Br H Cl Z1.010 H H H B1 Cl H I H Cl Z1.011 H H H B1 Cl H CHF₂ H ClZ1.012 H H H B1 Cl H CF₃ H Cl Z1.013 H H H B1 Cl H C≡C—H H Cl Z1.014 H HH B1 Cl H C≡C—Me H Cl Z1.015 H H H B1 Cl H C≡C—Si(Me)₃ H Cl Z1.016 H H HB1 Cl H C≡C-t-Bu H Cl Z1.017 H H H B1 Cl H C≡C-i-Pr H Cl Z1.018 H H H B1Cl H C≡C—CH₂OMe H Cl Z1.019 H H H B1 Cl H C≡C-p-Cl-phenyl H Cl Z1.020 HH H B1 Cl H p-Cl-phenyl H Cl Z1.021 H H H B1 Cl H CHO H Cl Z1.022 H H HB1 Cl H CH═NOMe H Cl Z1.023 H H H B1 Cl H COMe H Cl Z1.024 H H H B1 Cl HC(Me)═NOMe H Cl Z1.025 H H H B1 Cl H NO₂ H Cl Z1.026 H H H B1 Cl H NH₂ HCl Z1.027 H H H B1 Cl H NHMe H Cl Z1.028 H H H B1 Cl H N(Me)₂ H ClZ1.029 H H H B1 Cl H NHCOMe H Cl Z1.030 H H H B1 Cl H N═CHNEt(Me) H ClZ1.031 H H H B1 Cl H OCF₃ H Cl Z1.032 H H H B1 Cl H OCH₂CH═CHCl₂ H ClZ1.033 H H H B1 Cl H p-Cl-phenoxy H Cl Z1.034 H H H B1 Cl Me Cl H ClZ1.035 H H H B1 Cl Cl Cl H Cl Z1.036 H H H B1 Cl H Cl Cl Cl Z1.037 H H HB1 Cl Cl Cl Cl Cl Z1.038 H H H B1 Cl H H H Me Z1.039 H H H B1 Cl H Cl HMe Z1.040 H H H B1 Cl H Br H Me Z1.041 H H H B1 Cl H CF₃ H Me Z1.042 H HH B1 Cl H C≡C—H H Me Z1.043 H H H B1 Cl H C≡C—CH₂OMe H Me Z1.044 H H HB1 Cl H C(Me)═NOMe H Me Z1.045 H H H B1 Cl H H H CHO Z1.046 H H H B1 ClH Cl H CHO Z1.047 H H H B1 Cl H Br H CHO Z1.048 H H H B1 Cl H CF₃ H CHOZ1.049 H H H B1 Cl H C≡C—H H CHO Z1.050 H H H B1 Cl H C≡C—CH₂OMe H CHOZ1.051 H H H B1 Cl H C(Me)═NOMe H CHO Z1.052 H H H B1 Cl H H H OMeZ1.053 H H H B1 Cl H Cl H OMe Z1.054 H H H B1 Cl H Br H OMe Z1.055 H H HB1 Cl H CF₃ H OMe Z1.056 H H H B1 Cl H C≡C—H H OMe Z1.057 H H H B1 Cl HC≡C—CH₂OMe H OMe Z1.058 H H H B1 Cl H C(Me)═NOMe H OMe Z1.059 H H H B1OMe H H H OMe Z1.060 H H H B1 OMe H Cl H OMe Z1.061 H H H B1 OMe H Br HOMe Z1.062 H H H B1 OMe H CF₃ H OMe Z1.063 H H H B1 OMe H C≡C—H H OMeZ1.064 H H H B1 OMe H C≡C—CH₂OMe H OMe Z1.065 H H H B1 OMe H C(Me)═NOMeH OMe Z1.066 H H H B1 Me H H H Me Z1.067 H H H B1 Me H Cl H Me Z1.068 HH H B1 Me H Br H Me Z1.069 H H H B1 Me H I H Me Z1.070 H H H B1 Me H CF₃H Me Z1.071 H H H B1 Me H C≡C—H H Me Z1.072 H H H B1 Me H Me H Me Z1.073H H H B1 Me H C≡C—CH₂OMe H Me Z1.074 H H H B1 Me H C(Me)═NOMe H MeZ1.075 H H H B1 Me H NO₂ H Me Z1.076 H H H B1 Me H NH₂ H Me Z1.077 H H HB1 Me H NHCOMe H Me Z1.078 H H H B1 Me H p-Cl-phenyl H Me Z1.079 H H HB1 Me H H H CHO Z1.080 H H H B1 Me H Cl H CHO Z1.081 H H H B1 Me H Br HCHO Z1.082 H H H B1 i-Pr H H H i-Pr Z1.083 H H H B1 i-Pr H Cl H i-PrZ1.084 H H H B1 i-Pr H Br H i-Pr Z1.085 H H H B1 t-Bu H H H t-Bu Z1.086H H H B1 t-Bu H Cl H t-Bu Z1.087 H H H B1 t-Bu H Br H t-Bu Z1.088 H H HB1 t-Bu H Me H t-Bu Z1.089 H H H B1 t-Bu H t-Bu H t-Bu Z1.090 H H H B1t-Bu H OMe H t-Bu Z1.091 H H H B1 Br H H H Br Z1.092 H H H B1 Br H Br HBr Z1.093 H H H B1 F H H H F Z1.094 H H H B1 F H Cl H F Z1.095 H H H B1F H Br H F Z1.096 H H H B1 I H H H I Z1.097 H H H B1 I H Cl H I Z1.098 HMe H B1 H H COMe H H Z1.099 H Me H B1 H F H F H Z1.100 H Me H B1 Me H ClH H Z1.101 H Me H B1 H Cl Cl H H Z1.102 H Me H B1 H t-Bu H t-Bu H Z1.103H Me H B1 Cl H Cl H H Z1.104 H Me H B1 Cl H H Cl H Z1.105 H Me H B1 Cl HH H Cl Z1.106 H Me H B1 H Cl Cl H H Z1.107 H Me H B1 H Cl H Cl H Z1.108H Me H B1 Cl H Cl H Cl Z1.109 H Me H B1 Cl H Br H Cl Z1.110 H Me H B1 ClH I H Cl Z1.111 H Me H B1 Cl H CHF₂ H Cl Z1.112 H Me H B1 Cl H CF₃ H ClZ1.113 H Me H B1 Cl H C≡C—H H Cl Z1.114 H Me H B1 Cl H C≡C—Me H ClZ1.115 H Me H B1 Cl H C≡C—Si(Me)₃ H Cl Z1.116 H Me H B1 Cl H C≡C-t-Bu HCl Z1.117 H Me H B1 Cl H C≡C—C-i-Pr H Cl Z1.118 H Me H B1 Cl HC≡C—CH₂OMe H Cl Z1.119 H Me H B1 Cl H C≡C-p-Cl-phenyl H Cl Z1.120 H Me HB1 Cl H p-Cl-phenyl H Cl Z1.121 H Me H B1 Cl H CHO H Cl Z1.122 H Me H B1Cl H CH═NOMe H Cl Z1.123 H Me H B1 Cl H COMe H Cl Z1.124 H Me H B1 Cl HC(Me)═NOMe H Cl Z1.125 H Me H B1 Cl H NO₂ H Cl Z1.126 H Me H B1 Cl H NH₂H Cl Z1.127 H Me H B1 Cl H NHMe H Cl Z1.128 H Me H B1 Cl H N(Me)₂ H ClZ1.129 H Me H B1 Cl H NHCOMe H Cl Z1.130 H Me H B1 Cl H N═CHNEt(Me) H ClZ1.131 H Me H B1 Cl H OCF₃ H Cl Z1.132 H Me H B1 Cl H OCH₂CH═CHCl₂ H ClZ1.133 H Me H B1 Cl H p-Cl-phenoxy H Cl Z1.134 H Me H B1 Cl Me Cl H ClZ1.135 H Me H B1 Cl Cl Cl H Cl Z1.136 H Me H B1 Cl H Cl Cl Cl Z1.137 HMe H B1 Cl Cl Cl Cl Cl Z1.138 H Me H B1 Cl H H H Me Z1.139 H Me H B1 ClH Cl H Me Z1.140 H Me H B1 Cl H Br H Me Z1.141 H Me H B1 Cl H CF₃ H MeZ1.142 H Me H B1 Cl H C≡C—H H Me Z1.143 H Me H B1 Cl H C≡C—CH₂OMe H MeZ1.144 H Me H B1 Cl H C(Me)═NOMe H Me Z1.145 H Me H B1 Cl H H H CHOZ1.146 H Me H B1 Cl H Cl H CHO Z1.147 H Me H B1 Cl H Br H CHO Z1.148 HMe H B1 Cl H CF₃ H CHO Z1.149 H Me H B1 Cl H C≡C—H H CHO Z1.150 H Me HB1 Cl H C≡C—CH₂OMe H CHO Z1.151 H Me H B1 Cl H C(Me)═NOMe H CHO Z1.152 HMe H B1 Cl H H H OMe Z1.153 H Me H B1 Cl H Cl H OMe Z1.154 H Me H B1 ClH Br H OMe Z1.155 H Me H B1 Cl H CF₃ H OMe Z1.156 H Me H B1 Cl H C≡C—H HOMe Z1.157 H Me H B1 Cl H C≡C—CH₂OMe H OMe Z1.158 H Me H B1 Cl HC(Me)═NOMe H OMe Z1.159 H Me H B1 OMe H H H OMe Z1.160 H Me H B1 OMe HCl H OMe Z1.161 H Me H B1 OMe H Br H OMe Z1.162 H Me H B1 OMe H CF₃ HOMe Z1.163 H Me H B1 OMe H C≡C—H H OMe Z1.164 H Me H B1 OMe H C≡C—CH₂OMeH OMe Z1.165 H Me H B1 OMe H C(Me)═NOMe H OMe Z1.166 H Me H B1 Me H H HMe Z1.167 H Me H B1 Me H Cl H Me Z1.168 H Me H B1 Me H Br H Me Z1.169 HMe H B1 Me H I H Me Z1.170 H Me H B1 Me H CF₃ H Me Z1.171 H Me H B1 Me HC≡C—H H Me Z1.172 H Me H B1 Me H Me H Me Z1.173 H Me H B1 Me HC≡C—CH₂OMe H Me Z1.174 H Me H B1 Me H C(Me)═NOMe H Me Z1.175 H Me H B1Me H NO₂ H Me Z1.176 H Me H B1 Me H NH₂ H Me Z1.177 H Me H B1 Me HNHCOMe H Me Z1.178 H Me H B1 Me H p-Cl-phenyl H Me Z1.179 H Me H B1 Me HH H CHO Z1.180 H Me H B1 Me H Cl H CHO Z1.181 H Me H B1 Me H Br H CHOZ1.182 H Me H B1 i-Pr H H H i-Pr Z1.183 H Me H B1 i-Pr H Cl H i-PrZ1.184 H Me H B1 i-Pr H Br H i-Pr Z1.185 H Me H B1 t-Bu H H H t-BuZ1.186 H Me H B1 t-Bu H Cl H t-Bu Z1.187 H Me H B1 t-Bu H Me H t-BuZ1.188 H Me H B1 t-Bu H t-Bu H t-Bu Z1.189 H Me H B1 t-Bu H p-Cl-phenylH t-Bu Z1.190 H Me H B1 H H CF₃ H H Z1.191 H Me H B1 H H Br H H Z1.192 HMe H B1 Br H H H Br Z1.193 H Me H B1 Br H Br H Br Z1.194 H Me H B1 F H HH F Z1.195 H Me H B1 F H Cl H F Z1.196 H Me H B1 F H Br H F Z1.197 H MeH B1 I H H H I Z1.198 H Me H B1 I H Cl H I Z1.199 H Me H B1 I H Br H IZ1.200 H Me H B1 I H I H I Z1.201 H Me Me B1 Cl H H H Cl Z1.202 H Me MeB1 Cl H Cl H Cl Z1.203 H Me Me B1 Br H H H Br Z1.204 H Me Me B1 Br H BrH Br Z1.205 H Me Me B1 Me H H H Me Z1.206 H Me Me B1 Me H Cl H Me Z1.207H Me Me B1 Me H Br H Me Z1.208 H Me H B1 Cl H H H Cl Z1.209 Me Me H B1Cl H Cl H Cl Z1.210 Me Me H B1 Br H H H Br Z1.211 Me Me H B1 Br H Br HBr Z1.212 Me Me H B1 Me H Cl H Me Z1.213 Me Me H B1 Me H Br H Me Z1.214i-Pr Me H B1 Me H H H Me Z1.215 c-Pr Me H B1 Me H H H Me Z1.216 Et Et HB1 Me H H H Me Z1.217 Et Et H B1 Me H Br H Me Z1.218 CH₂CH₂ H B1 Cl H HH H Z1.219 CH₂CH₂ H B1 Me H H H Me Z1.220 CH₂CH₂ H B1 Me H Br H MeZ1.221 CH₂CH₂ H B1 H H Cl H H Z1.222 CH₂CH₂ H B1 Cl H Cl H H Z1.223CH₂CH₂ H B1 Cl H H H Cl Z1.224 CH₂CH₂ H B1 Cl H Cl H Cl Z1.225 CH₂CH₂ HB1 Br H H H Br Z1.226 CH₂CH₂ H B1 Br H Br H Br Z1.227 H CH₂ B1 Me H H HMe Z1.228 H CH₂ B1 Me H Br H Me Z1.229 H CH₂ B1 H H Cl H H Z1.230 H CH₂B1 Cl H Cl H H Z1.231 H CH₂ B1 Cl H H H Cl Z1.232 H CH₂ B1 Cl H Cl H ClZ1.233 H CH₂ B1 Br H H H Br Z1.234 H CH₂ B1 Br H Br H Br Z1.235 H H H B2Cl H Cl H — Z1.236 H H H B2 Cl H Br H — Z1.237 H H H B2 Br H Br H —Z1.238 H H H B2 Cl H CF₃ H — Z1.239 H Me H B2 Cl H CF₃ H — Z1.240 H Et HB2 Cl H CF₃ H — Z1.241 Me Me H B2 Cl H CF₃ H — Z1.242 H H Me B2 Cl H CF₃H — Z1.243 H Et H B2 Cl H CF₃ H — Z1.244 CH₂CH₂ H B2 Cl H CF₃ H — Z1.245H CH₂ B2 Cl H CF₃ H — Z1.246 H H H B3 Cl H H Cl — Z1.247 H H H B3 Cl H HBr — Z1.248 H H H B3 Cl H H I — Z1.249 H H H B3 Cl H H Me — Z1.250 H H HB3 Me H H Cl — Z1.251 H H H B3 Me H H Br — Z1.252 H H H B3 Me H H Me —Z1.253 H Me H B3 Cl H H Cl — Z1.254 H Me H B3 Me H H Cl — Z1.255 H H HB4 Cl H H Cl — Z1.256 H H H B4 Br H H Br — Z1.247 H H H B4 Me H H Me —Z1.258 H Me H B4 Cl H H Cl — Z1.259 H Me H B4 Br H H Br — Z1.260 H Me HB4 Me H H Me — Z1.261 H H H B5 Me H Me — — Z1.262 H H H B5 Me H Me — —Z1.263 H H H B5 H Me H — — Z1.264 H H H B5 H Cl H — — Z1.265 H H H B5 HBr H — — Z1.266 H H H B5 H CF₃ H — — Z1.267 H Me H B5 Me H Me — — Z1.268H Me H B5 Me H Me — — Z1.269 H Me H B5 H Me H — — Z1.270 H Me H B5 H ClH — — Z1.271 H Me H B5 H Br H — — Z1.272 H Me H B5 H CF₃ H — — Z1.273 HH H B20 Cl H H H H Z1.274 H H H B20 Cl H Cl H H Z1.275 H H H B20 Br H HH H Z1.276 H H H B20 Br H Br H H Z1.277 H H H B20 Me H H H H Z1.278 H HH B20 CF₃ H H H H Z1.279 H H H B20 COMe H H H H Z1.280 H H H B20 Cl H HCl H Z1.281 H Me H B20 Cl H H H H Z1.282 H Me H B20 Cl H Cl H H Z1.283 HMe H B20 Br H H H H Z1.284 H Me H B20 Br H Br H H Z1.285 H Me H B20 Me HH H H Z1.286 H Me H B20 CF₃ H H H H Z1.287 H Me H B20 COMe H H H HZ1.288 H Me H B20 Cl H H Cl H Z1.289 H H H B21 Cl H H H H Z1.290 H H HB21 H Cl H H H Z1.291 H H H B21 Cl Cl H H H Z1.292 H H H B21 H H H Cl HZ1.293 H H H B21 Cl H H Cl H Z1.294 H H H B21 H Cl H Cl H Z1.295 H H HB21 Cl Cl H Cl H Z1.296 H H H B21 Br H H H H Z1.297 H H H B21 CF₃ H H HH Z1.298 H H H B21 Me H H H H Z1.299 H H H B21 Cl H H H H Z1.300 H H HB21 Br H H Cl H Z1.301 H H H B21 CF₃ H H Cl H Z1.302 H H H B21 Me H H ClH Z1.303 H H H B21 Cl H H Cl H Z1.304 H Me H B21 Cl H H H H Z1.305 H MeH B21 H Cl H H H Z1.306 H Me H B21 Cl Cl H H H Z1.307 H Me H B21 H H HCl H Z1.308 H Me H B21 Cl H H Cl H Z1.309 H Me H B21 H Cl H Cl H Z1.310H Me H B21 Cl Cl H Cl H Z1.311 H Me H B21 Br H H H H Z1.312 H Me H B21CF₃ H H H H Z1.313 H Me H B21 Me H H H H Z1.314 H Me H B21 Cl H H H HZ1.315 H Me H B21 Br H H Cl H Z1.316 H Me H B21 CF₃ H H Cl H Z1.317 H MeH B21 Me H H Cl H Z1.318 H Me H B21 Cl H H Cl H Z1.319 H H H B22 Me H HH H Z1.320 H H H B22 H H H H Cl Z1.321 H H H B22 Me H H H Cl Z1.322 H HH B22 H H H Cl Cl Z1.323 H H H B22 H H H NO₂ Cl Z1.324 H H H B22 H H HMe Cl Z1.325 H H H B22 H H H H Br Z1.326 H H H B22 H H H Cl Br Z1.327 HH H B22 H H H Me Br Z1.328 H H H B22 H H H Br Br Z1.329 H Me H B22 Me HH H H Z1.330 H Me H B22 H H H H Cl Z1.331 H Me H B22 Me H H H Cl Z1.332H Me H B22 H H H Cl Cl Z1.333 H Me H B22 H H H NO₂ Cl Z1.334 H Me H B22H H H Me Cl Z1.335 H Me H B22 H H H H Br Z1.336 H Me H B22 H H H Cl BrZ1.337 H Me H B22 H H H Me Br Z1.338 H Me H B22 H H H Br Br Z1.339 H H HB23 Cl H H H H Z1.340 H H H B23 Cl Cl H H H Z1.341 H H H B23 Cl Me H H HZ1.342 H H H B23 Me H H H H Z1.343 H H H B23 Me Cl H H H Z1.344 H H HB23 Me Me H H H Z1.345 H H H B23 H H H H Me Z1.346 H H H B23 Cl H H H MeZ1.347 H H H B23 Me H H H Me Z1.348 H Me H B23 Cl H H H H Z1.349 H Me HB23 Cl Cl H H H Z1.350 H Me H B23 Cl Me H H H Z1.351 H Me H B23 Me H H HH Z1.352 H Me H B23 Me Cl H H H Z1.353 H Me H B23 Me Me H H H Z1.354 HMe H B23 H H H H Me Z1.355 H Me H B23 Cl H H H Me Z1.356 H Me H B23 Me HH H Me Z1.357 H H H B24 Cl H H H H Z1.358 H H H B24 Br H H H H Z1.359 HH H B24 CN H H H H Z1.360 H H H B24 Me H H H H Z1.361 H H H B24 OMe H HH H Z1.362 H H H B24 Cl H Cl H H Z1.363 H H H B24 Br H Cl H H Z1.364 H HH B24 CN H Cl H H Z1.365 H H H B24 Me H Cl H H Z1.366 H H H B24 OMe H ClH H Z1.367 H H H B24 Cl H F H H Z1.368 H H H B24 Br H F H H Z1.369 H H HB24 CN H F H H Z1.370 H H H B24 Me H F H H Z1.371 H H H B24 OMe H F H HZ1.372 H H H B24 Cl H H H F Z1.373 H Me H B24 Cl H H H H Z1.374 H Me HB24 Br H H H H Z1.375 H Me H B24 CN H H H H Z1.376 H Me H B24 Me H H H HZ1.377 H Me H B24 OMe H H H H Z1.378 H Me H B24 Cl H Cl H H Z1.379 H MeH B24 Br H Cl H H Z1.380 H Me H B24 CN H Cl H H Z1.381 H Me H B24 Me HCl H H Z1.382 H Me H B24 OMe H Cl H H Z1.383 H Me H B24 Cl H F H HZ1.384 H Me H B24 Br H F H H Z1.385 H Me H B24 CN H F H H Z1.386 H Me HB24 Me H F H H Z1.387 H Me H B24 OMe H F H H Z1.388 H Me H B24 Cl H H HF Z1.389 H Me H B25 Me H H H H Z1.390 H Me H B25 Cl H H H H Z1.391 H MeH B25 OMe H H H H Z1.392 H Me H B26 Me H H H H Z1.393 H Me H B26 Cl H HH H Z1.394 H Me H B26 OMe H H H H Z1.395 H Me H B28 H H Me Me H Z1.396 HMe H B28 Me Me Me Me H Z1.397 H Me H B29 H H H Me Me Z1.398 H Me H B29Me Me H Me Me

Table 8a: Compounds of Formula IIB

The invention is further illustrated by the preferred individualcompounds of formula (IIB)

wherein B is one of the preferred groups B1 to B5 or B20 to B26, B28 orB29

The compound of formula (IIB) are listed below in Table 8a.

TABLE 8A Cpd No. R₂ R₁ R₃ B R₁₀ R₁₁ R₁₂ R₁₃ R₁₄ Z1a.001 H H H B1 Cl H HH H Z1a.002 H H H B1 Cl Cl H H H Z1a.003 H H H B1 Cl H Cl H H Z1a.004 HH H B1 Cl H H Cl H Z1a.005 H H H B1 Cl H H H Cl Z1a.006 H H H B1 H Cl ClH H Z1a.007 H H H B1 H Cl H Cl H Z1a.008 H H H B1 Cl H Cl H Cl Z1a.009 HH H B1 Cl H Br H Cl Z1a.010 H H H B1 Cl H I H Cl Z1a.011 H H H B1 Cl HCHF₂ H Cl Z1a.012 H H H B1 Cl H CF₃ H Cl Z1a.013 H H H B1 Cl H C≡C—H HCl Z1a.014 H H H B1 Cl H C≡C-Me H Cl Z1a.015 H H H B1 Cl H C≡C—Si(Me)₃ HCl Z1a.016 H H H B1 Cl H C≡C-t-Bu H Cl Z1a.017 H H H B1 Cl H C≡C-i-Pr HCl Z1a.018 H H H B1 Cl H C≡C—CH₂OMe H Cl Z1a.019 H H H B1 Cl HC≡C-p-Cl-phenyl H Cl Z1a.020 H H H B1 Cl H p-Cl-phenyl H Cl Z1a.021 H HH B1 Cl H CHO H Cl Z1a.022 H H H B1 Cl H CH═NOMe H Cl Z1a.023 H H H B1Cl H COMe H Cl Z1a.024 H H H B1 Cl H C(Me)═NOMe H Cl Z1a.025 H H H B1 ClH NO₂ H Cl Z1a.026 H H H B1 Cl H NH₂ H Cl Z1a.027 H H H B1 Cl H NHMe HCl Z1a.028 H H H B1 Cl H N(Me)₂ H Cl Z1a.029 H H H B1 Cl H NHCOMe H ClZ1a.030 H H H B1 Cl H N═CHNEt(Me) H Cl Z1a.031 H H H B1 Cl H OCF₃ H ClZ1a.032 H H H B1 Cl H OCH₂CH═CHCl₂ H Cl Z1a.033 H H H B1 Cl Hp-Cl-phenoxy H Cl Z1a.034 H H H B1 Cl Me Cl H Cl Z1a.035 H H H B1 Cl ClCl H Cl Z1a.036 H H H B1 Cl H Cl Cl Cl Z1a.037 H H H B1 Cl Cl Cl Cl ClZ1a.038 H H H B1 Cl H H H Me Z1a.039 H H H B1 Cl H Cl H Me Z1a.040 H H HB1 Cl H Br H Me Z1a.041 H H H B1 Cl H CF₃ H Me Z1a.042 H H H B1 Cl HC≡C—H H Me Z1a.043 H H H B1 Cl H C≡C—CH₂OMe H Me Z1a.044 H H H B1 Cl HC(Me)═NOMe H Me Z1a.045 H H H B1 Cl H H H CHO Z1a.046 H H H B1 Cl H Cl HCHO Z1a.047 H H H B1 Cl H Br H CHO Z1a.048 H H H B1 Cl H CF₃ H CHOZ1a.049 H H H B1 Cl H C≡C—H H CHO Z1a.050 H H H B1 Cl H C≡C—CH₂OMe H CHOZ1a.051 H H H B1 Cl H C(Me)═NOMe H CHO Z1a.052 H H H B1 Cl H H H OMeZ1a.053 H H H B1 Cl H Cl H OMe Z1a.054 H H H B1 Cl H Br H OMe Z1a.055 HH H B1 Cl H CF₃ H OMe Z1a.056 H H H B1 Cl H C≡C—H H OMe Z1a.057 H H H B1Cl H C≡C—CH₂OMe H OMe Z1a.058 H H H B1 Cl H C(Me)═NOMe H OMe Z1a.059 H HH B1 OMe H H H OMe Z1a.060 H H H B1 OMe H Cl H OMe Z1a.0B1 H H H B1 OMeH Br H OMe Z1a.062 H H H B1 OMe H CF₃ H OMe Z1a.063 H H H B1 OMe H C≡C—HH OMe Z1a.064 H H H B1 OMe H C≡C—CH₂OMe H OMe Z1a.065 H H H B1 OMe HC(Me)═NOMe H OMe Z1a.066 H H H B1 Me H H H Me Z1a.067 H H H B1 Me H Cl HMe Z1a.068 H H H B1 Me H Br H Me Z1a.069 H H H B1 Me H I H Me Z1a.070 HH H B1 Me H CF₃ H Me Z1a.071 H H H B1 Me H C≡C—H H Me Z1a.072 H H H B1Me H Me H Me Z1a.073 H H H B1 Me H C≡C—CH₂OMe H Me Z1a.074 H H H B1 Me HC(Me)═NOMe H Me Z1a.075 H H H B1 Me H NO₂ H Me Z1a.076 H H H B1 Me H NH₂H Me Z1a.077 H H H B1 Me H NHCOMe H Me Z1a.078 H H H B1 Me H p-Cl-phenylH Me Z1a.079 H H H B1 Me H H H CHO Z1a.080 H H H B1 Me H Cl H CHOZ1a.081 H H H B1 Me H Br H CHO Z1a.082 H H H B1 i-Pr H H H i-Pr Z1a.083H H H B1 i-Pr H Cl H i-Pr Z1a.084 H H H B1 i-Pr H Br H i-Pr Z1a.085 H HH B1 t-Bu H H H t-Bu Z1a.086 H H H B1 t-Bu H Cl H t-Bu Z1a.087 H H H B1t-Bu H Br H t-Bu Z1a.088 H H H B1 t-Bu H Me H t-Bu Z1a.089 H H H B1 t-BuH t-Bu H t-Bu Z1a.090 H H H B1 t-Bu H OMe H t-Bu Z1a.091 H H H B1 Br H HH Br Z1a.092 H H H B1 Br H Br H Br Z1a.093 H H H B1 F H H H F Z1a.094 HH H B1 F H Cl H F Z1a.095 H H H B1 F H Br H F Z1a.096 H H H B1 I H H H IZ1a.097 H H H B1 I H Cl H I Z1a.098 H Me H B1 H H COMe H H Z1a.099 H MeH B1 H F H F H Z1a.100 H Me H B1 Me H Cl H H Z1a.101 H Me H B1 H Cl Cl HH Z1a.102 H Me H B1 H t-Bu H t-Bu H Z1a.103 H Me H B1 Cl H Cl H HZ1a.104 H Me H B1 Cl H H Cl H Z1a.105 H Me H B1 Cl H H H Cl Z1a.106 H MeH B1 H Cl Cl H H Z1a.107 H Me H B1 H Cl H Cl H Z1a.108 H Me H B1 Cl H ClH Cl Z1a.109 H Me H B1 Cl H Br H Cl Z1a.110 H Me H B1 Cl H I H ClZ1a.111 H Me H B1 Cl H CHF₂ H Cl Z1a.112 H Me H B1 Cl H CF₃ H Cl Z1a.113H Me H B1 Cl H C≡C—H H Cl Z1a.114 H Me H B1 Cl H C≡C-Me H Cl Z1a.115 HMe H B1 Cl H C≡C—Si(Me)₃ H Cl Z1a.116 H Me H B1 Cl H C≡C-t-Bu H ClZ1a.117 H Me H B1 Cl H C≡C—C-i-Pr H Cl Z1a.118 H Me H B1 Cl H C≡C—CH₂OMeH Cl Z1a.119 H Me H B1 Cl H C≡C-p-Cl-phenyl H Cl Z1a.120 H Me H B1 Cl Hp-Cl-phenyl H Cl Z1a.121 H Me H B1 Cl H CHO H Cl Z1a.122 H Me H B1 Cl HCH═NOMe H Cl Z1a.123 H Me H B1 Cl H COMe H Cl Z1a.124 H Me H B1 Cl HC(Me)═NOMe H Cl Z1a.125 H Me H B1 Cl H NO₂ H Cl Z1a.126 H Me H B1 Cl HNH₂ H Cl Z1a.127 H Me H B1 Cl H NHMe H Cl Z1a.128 H Me H B1 Cl H N(Me)₂H Cl Z1a.129 H Me H B1 Cl H NHCOMe H Cl Z1a.130 H Me H B1 Cl HN═CHNEt(Me) H Cl Z1a.131 H Me H B1 Cl H OCF₃ H Cl Z1a.132 H Me H B1 Cl HOCH₂CH═CHCl₂ H Cl Z1a.133 H Me H B1 Cl H p-Cl-phenoxy H Cl Z1a.134 H MeH B1 Cl Me Cl H Cl Z1a.135 H Me H B1 Cl Cl Cl H Cl Z1a.136 H Me H B1 ClH Cl Cl Cl Z1a.137 H Me H B1 Cl Cl Cl Cl Cl Z1a.138 H Me H B1 Cl H H HMe Z1a.139 H Me H B1 Cl H Cl H Me Z1a.140 H Me H B1 Cl H Br H Me Z1a.141H Me H B1 Cl H CF₃ H Me Z1a.142 H Me H B1 Cl H C≡C—H H Me Z1a.143 H Me HB1 Cl H C≡C—CH₂OMe H Me Z1a.144 H Me H B1 Cl H C(Me)═NOMe H Me Z1a.145 HMe H B1 Cl H H H CHO Z1a.146 H Me H B1 Cl H Cl H CHO Z1a.147 H Me H B1Cl H Br H CHO Z1a.148 H Me H B1 Cl H CF₃ H CHO Z1a.149 H Me H B1 Cl HC≡C—H H CHO Z1a.150 H Me H B1 Cl H C≡C—CH₂OMe H CHO Z1a.151 H Me H B1 ClH C(Me)═NOMe H CHO 21a.152 H Me H B1 Cl H H H OMe Z1a.153 H Me H B1 Cl HCl H OMe Z1a.154 H Me H B1 Cl H Br H OMe Z1a.155 H Me H B1 Cl H CF₃ HOMe Z1a.156 H Me H B1 Cl H C≡C—H H OMe Z1a.157 H Me H B1 Cl H C≡C—CH₂OMeH OMe Z1a.158 H Me H B1 Cl H C(Me)═NOMe H OMe Z1a.159 H Me H B1 OMe H HH OMe Z1a.160 H Me H B1 OMe H Cl H OMe Z1a.1B1 H Me H B1 OMe H Br H OMeZ1a.162 H Me H B1 OMe H CF₃ H OMe Z1a.163 H Me H B1 OMe H C═C—H H OMeZ1a.164 H Me H B1 OMe H C≡C—CH₂OMe H OMe Z1a.165 H Me H B1 OMe HC(Me)═NOMe H OMe Z1a.166 H Me H B1 Me H H H Me Z1a.167 H Me H B1 Me H ClH Me Z1a.168 H Me H B1 Me H Br H Me Z1a.169 H Me H B1 Me H I H MeZ1a.170 H Me H B1 Me H CF₃ H Me Z1a.171 H Me H B1 Me H C≡C—H H MeZ1a.172 H Me H B1 Me H Me H Me Z1a.173 H Me H B1 Me H C≡C—CH₂OMe H MeZ1a.174 H Me H B1 Me H C(Me)═NOMe H Me Z1a.175 H Me H B1 Me H NO₂ H MeZ1a.176 H Me H B1 Me H NH₂ H Me Z1a.177 H Me H B1 Me H NHCOMe H MeZ1a.178 H Me H B1 Me H p-Cl-phenyl H Me Z1a.179 H Me H B1 Me H H H CHOZ1a.180 H Me H B1 Me H Cl H CHO Z1a.181 H Me H B1 Me H Br H CHO Z1a.182H Me H B1 i-Pr H H H i-Pr Z1a.183 H Me H B1 i-Pr H Cl H i-Pr Z1a.184 HMe H B1 i-Pr H Br H i-Pr Z1a.185 H Me H B1 t-Bu H H H t-Bu Z1a.186 H MeH B1 t-Bu H Cl H t-Bu Z1a.187 H Me H B1 t-Bu H Me H t-Bu Z1a.188 H Me HB1 t-Bu H t-Bu H t-Bu Z1a.189 H Me H B1 t-Bu H p-Cl-phenyl H t-BuZ1a.190 H Me H B1 H H CF₃ H H Z1a.191 H Me H B1 H H Br H H Z1a.192 H MeH B1 Br H H H Br Z1a.193 H Me H B1 Br H Br H Br Z1a.194 H Me H B1 F H HH F Z1a.195 H Me H B1 F H Cl H F Z1a.196 H Me H B1 F H Br H F Z1a.197 HMe H B1 I H H H I Z1a.198 H Me H B1 I H Cl H I Z1a.199 H Me H B1 I H BrH I Z1a.200 H Me H B1 I H I H I Z1a.201 H Me Me B1 Cl H H H Cl Z1a.202 HMe Me B1 Cl H Cl H Cl Z1a.203 H Me Me B1 Br H H H Br Z1a.204 H Me Me B1Br H Br H Br Z1a.205 H Me Me B1 Me H H H Me Z1a.206 H Me Me B1 Me H Cl HMe Z1a.207 H Me Me B1 Me H Br H Me Z1a.208 H Me H B1 Cl H H H Cl Z1a.209Me Me H B1 Cl H Cl H Cl Z1a.210 Me Me H B1 Br H H H Br Z1a.211 Me Me HB1 Br H Br H Br Z1a.212 Me Me H B1 Me H Cl H Me Z1a.213 Me Me H B1 Me HBr H Me Z1a.214 i-Pr Me H B1 Me H H H Me Z1a.215 c-Pr Me H B1 Me H H HMe Z1a.216 Et Et H B1 Me H H H Me Z1a.217 Et Et H B1 Me H Br H MeZ1a.218 CH₂CH₂ H B1 Cl H H H H Z1a.219 CH₂CH₂ H B1 Me H H H Me Z1a.220CH₂CH₂ H B1 Me H Br H Me Z1a.221 CH₂CH₂ H B1 H H Cl H H Z1a.222 CH₂CH₂ HB1 Cl H Cl H H Z1a.223 CH₂CH₂ H B1 Cl H H H Cl Z1a.224 CH₂CH₂ H B1 Cl HCl H Cl Z1a.225 CH₂CH₂ H B1 Br H H H Br Z1a.226 CH₂CH₂ H B1 Br H Br H BrZ1a.227 H CH₂ B1 Me H H H Me Z1a.228 H CH₂ B1 Me H Br H Me Z1a.229 H CH₂B1 H H Cl H H Z1a.230 H CH₂ B1 Cl H Cl H H Z1a.231 H CH₂ B1 Cl H H H ClZ1a.232 H CH₂ B1 Cl H Cl H Cl Z1a.233 H CH₂ B1 Br H H H Br Z1a.234 H CH₂B1 Br H Br H Br Z1a.235 H H H B2 Cl H Cl H — Z1a.236 H H H B2 Cl H Br H— Z1a.237 H H H B2 Br H Br H — Z1a.238 H H H B2 Cl H CF₃ H — Z1a.239 HMe H B2 Cl H CF₃ H — Z1a.240 H Et H B2 Cl H CF₃ H — Z1a.241 Me Me H B2Cl H CF₃ H — Z1a.242 H H Me B2 Cl H CF₃ H — Z1a.243 H Et H B2 Cl H CF₃ H— Z1a.244 CH₂CH₂ H B2 Cl H CF₃ H — Z1a.245 H CH₂ B2 Cl H CF₃ H — Z1a.246H H H B3 Cl H H Cl — Z1a.247 H H H B3 Cl H H Br — Z1a.248 H H H B3 Cl HH I — Z1a.249 H H H B3 Cl H H Me — Z1a.250 H H H B3 Me H H Cl — Z1a.251H H H B3 Me H H Br — Z1a.252 H H H B3 Me H H Me — Z1a.253 H Me H B3 Cl HH Cl — Z1a.254 H Me H B3 Me H H Cl — Z1a.255 H H H B4 Cl H H Cl —Z1a.256 H H H B4 Br H H Br — Z1a.247 H H H B4 Me H H Me — Z1a.258 H Me HB4 Cl H H Cl — Z1a.259 H Me H B4 Br H H Br — Z1a.260 H Me H B4 Me H H Me— Z1a.261 H H H B5 Me H Me — — Z1a.262 H H H B5 Me H Me — — Z1a.263 H HH B5 H Me H — — Z1a.264 H H H B5 H Cl H — — Z1a.265 H H H B5 H Br H — —Z1a.266 H H H B5 H CF₃ H — — Z1a.267 H Me H B5 Me H Me — — Z1a.268 H MeH B5 Me H Me — — Z1a.269 H Me H B5 H Me H — — Z1a.270 H Me H B5 H Cl H —— Z1a.271 H Me H B5 H Br H — — Z1a.272 H Me H B5 H CF₃ H — — Z1a.273 H HH B20 Cl H H H H Z1a.274 H H H B20 Cl H Cl H H Z1a.275 H H H B20 Br H HH H Z1a.276 H H H B20 Br H Br H H Z1a.277 H H H B20 Me H H H H Z1a.278 HH H B20 CF₃ H H H H Z1a.279 H H H B20 COMe H H H H Z1a.280 H H H B20 ClH H Cl H Z1a.281 H Me H B20 Cl H H H H Z1a.282 H Me H B20 Cl H Cl H HZ1a.283 H Me H B20 Br H H H H Z1a.284 H Me H B20 Br H Br H H Z1a.285 HMe H B20 Me H H H H Z1a.286 H Me H B20 CF₃ H H H H Z1a.287 H Me H B20COMe H H H H Z1a.288 H Me H B20 Cl H H Cl H Z1a.289 H H H B21 Cl H H H HZ1a.290 H H H B21 H Cl H H H Z1a.291 H H H B21 Cl Cl H H H Z1a.292 H H HB21 H H H Cl H Z1a.293 H H H B21 Cl H H Cl H Z1a.294 H H H B21 H Cl H ClH Z1a.295 H H H B21 Cl Cl H Cl H Z1a.296 H H H B21 Br H H H H Z1a.297 HH H B21 CF₃ H H H H Z1a.298 H H H B21 Me H H H H Z1a.299 H H H B21 Cl HH H H Z1a.300 H H H B21 Br H H Cl H Z1a.301 H H H B21 CF₃ H H Cl HZ1a.302 H H H B21 Me H H Cl H Z1a.303 H H H B21 Cl H H Cl H Z1a.304 H MeH B21 Cl H H H H Z1a.305 H Me H B21 H Cl H H H Z1a.306 H Me H B21 Cl ClH H H Z1a.307 H Me H B21 H H H Cl H Z1a.308 H Me H B21 Cl H H Cl HZ1a.309 H Me H B21 H Cl H Cl H Z1a.310 H Me H B21 Cl Cl H Cl H Z1a.311 HMe H B21 Br H H H H Z1a.312 H Me H B21 CF₃ H H H H Z1a.313 H Me H B21 MeH H H H Z1a.314 H Me H B21 Cl H H H H Z1a.315 H Me H B21 Br H H Cl HZ1a.316 H Me H B21 CF₃ H H Cl H Z1a.317 H Me H B21 Me H H Cl H Z1a.318 HMe H B21 Cl H H Cl H Z1a.319 H H H B22 Me H H H H Z1a.320 H H H B22 H HH H Cl Z1a.321 H H H B22 Me H H H Cl Z1a.322 H H H B22 H H H Cl ClZ1a.323 H H H B22 H H H NO₂ Cl Z1a.324 H H H B22 H H H Me Cl Z1a.325 H HH B22 H H H H Br Z1a.326 H H H B22 H H H Cl Br Z1a.327 H H H B22 H H HMe Br Z1a.328 H H H B22 H H H Br Br Z1a.329 H Me H B22 Me H H H HZ1a.330 H Me H B22 H H H H Cl Z1a.331 H Me H B22 Me H H H Cl Z1a.332 HMe H B22 H H H Cl Cl Z1a.333 H Me H B22 H H H NO₂ Cl Z1a.334 H Me H B22H H H Me Cl Z1a.335 H Me H B22 H H H H Br Z1a.336 H Me H B22 H H H Cl BrZ1a.337 H Me H B22 H H H Me Br Z1a.338 H Me H B22 H H H Br Br Z1a.339 HH H B23 Cl H H H H Z1a.340 H H H B23 Cl Cl H H H Z1a.341 H H H B23 Cl MeH H H Z1a.342 H H H B23 Me H H H H Z1a.343 H H H B23 Me Cl H H H Z1a.344H H H B23 Me Me H H H Z1a.345 H H H B23 H H H H Me Z1a.346 H H H B23 ClH H H Me Z1a.347 H H H B23 Me H H H Me Z1a.348 H Me H B23 Cl H H H HZ1a.349 H Me H B23 Cl Cl H H H Z1a.350 H Me H B23 Cl Me H H H Z1a.351 HMe H B23 Me H H H H Z1a.352 H Me H B23 Me Cl H H H Z1a.353 H Me H B23 MeMe H H H Z1a.354 H Me H B23 H H H H Me Z1a.355 H Me H B23 Cl H H H MeZ1a.356 H Me H B23 Me H H H Me Z1a.357 H H H B24 Cl H H H H Z1a.358 H HH B24 Br H H H H Z1a.359 H H H B24 CN H H H H Z1a.360 H H H B24 Me H H HH Z1a.361 H H H B24 OMe H H H H Z1a.362 H H H B24 Cl H Cl H H Z1a.363 HH H B24 Br H Cl H H Z1a.364 H H H B24 CN H Cl H H Z1a.365 H H H B24 Me HCl H H Z1a.366 H H H B24 OMe H Cl H H Z1a.367 H H H B24 Cl H F H HZ1a.368 H H H B24 Br H F H H Z1a.369 H H H B24 CN H F H H Z1a.370 H H HB24 Me H F H H Z1a.371 H H H B24 OMe H F H H Z1a.372 H H H B24 Cl H H HF Z1a.373 H Me H B24 Cl H H H H Z1a.374 H Me H B24 Br H H H H Z1a.375 HMe H B24 CN H H H H Z1a.376 H Me H B24 Me H H H H Z1a.377 H Me H B24 OMeH H H H Z1a.378 H Me H B24 Cl H Cl H H Z1a.379 H Me H B24 Br H Cl H HZ1a.380 H Me H B24 CN H Cl H H Z1a.381 H Me H B24 Me H Cl H H Z1a.382 HMe H B24 OMe H Cl H H Z1a.383 H Me H B24 Cl H F H H Z1a.384 H Me H B24Br H F H H Z1a.385 H Me H B24 CN H F H H Z1a.386 H Me H B24 Me H F H HZ1a.387 H Me H B24 OMe H F H H Z1a.388 H Me H B24 Cl H H H F Z1a.389 HMe H B25 Me H H H H Z1a.390 H Me H B25 Cl H H H H Z1a.391 H Me H B25 OMeH H H H Z1a.392 H Me H B26 Me H H H H Z1a.393 H Me H B26 Cl H H H HZ1a.394 H Me H B26 OMe H H H H Z1a.395 H Me H B28 H H Me Me H Z1a.396 HMe H B28 Me Me Me Me H Z1a.397 H Me H B29 H H H Me Me Z1a.398 H Me H B29Me Me H Me Me

Table 9 Compounds of Formula IVA

The invention is further illustrated by the preferred individualcompounds of formula (IVA)

wherein B is one of the preferred groups B1 to B5 or B20 to B26, B28 orB29:

The compound of formula IVA are listed below in Table 9. Characterisingdata is given in Table 12.

TABLE 9 Cpd No. R₁ R₃ B R₁₀ R₁₁ R₁₂ R₁₃ R₁₄ Z2.001 H H B1 Cl H H H HZ2.002 H H B1 Cl Cl H H H Z2.003 H H B1 Cl H Cl H H Z2.004 H H B1 Cl H HCl H Z2.005 H H B1 Cl H H H Cl Z2.006 H H B1 H Cl Cl H H Z2.007 H H B1 HCl H Cl H Z2.008 H H B1 Cl H Cl H Cl Z2.009 H H B1 Cl H Br H Cl Z2.010 HH B1 Cl H I H Cl Z2.011 H H B1 Cl H CHF₂ H Cl Z2.012 H H B1 Cl H CF₃ HCl Z2.013 H H B1 Cl H C≡C—H H Cl Z2.014 H H B1 Cl H C≡C-Me H Cl Z2.015 HH B1 Cl H C≡C—Si(Me)₃ H Cl Z2.016 H H B1 Cl H C≡C-t-Bu H Cl Z2.017 H HB1 Cl H C≡C-i-Pr H Cl Z2.018 H H B1 Cl H C≡C—CH₂OMe H Cl Z2.019 H H B1Cl H C≡C-p-Cl-phenyl H Cl Z2.020 H H B1 Cl H p-Cl-phenyl H Cl Z2.021 H HB1 Cl H CHO H Cl Z2.022 H H B1 Cl H CH═NOMe H Cl Z2.023 H H B1 Cl H COMeH Cl Z2.024 H H B1 Cl H C(Me)═NOMe H Cl Z2.025 H H B1 Cl H NO₂ H ClZ2.026 H H B1 Cl H NH₂ H Cl Z2.027 H H B1 Cl H NHMe H Cl Z2.028 H H B1Cl H N(Me)₂ H Cl Z2.029 H H B1 Cl H NHCOMe H Cl Z2.030 H H B1 Cl HN═CHNEt(Me) H Cl Z2.031 H H B1 Cl H OCF₃ H Cl Z2.032 H H B1 Cl HOCH₂CH═CHCl₂ H Cl Z2.033 H H B1 Cl H p-Cl-phenoxy H Cl Z2.034 H H B1 ClMe Cl H Cl Z2.035 H H B1 Cl Cl Cl H Cl Z2.036 H H B1 Cl H Cl Cl ClZ2.037 H H B1 Cl Cl Cl Cl Cl Z2.038 H H B1 Cl H H H Me Z2.039 H H B1 ClH Cl H Me Z2.040 H H B1 Cl H Br H Me Z2.041 H H B1 Cl H CF₃ H Me Z2.042H H B1 Cl H C≡C—H H Me Z2.043 H H B1 Cl H C≡C—CH₂OMe H Me Z2.044 H H B1Cl H C(Me)═NOMe H Me Z2.045 H H B1 Cl H H H CHO Z2.046 H H B1 Cl H Cl HCHO Z2.047 H H B1 Cl H Br H CHO Z2.048 H H B1 Cl H CF₃ H CHO Z2.049 H HB1 Cl H C≡C—H H CHO Z2.050 H H B1 Cl H C≡C—CH₂OMe H CHO Z2.051 H H B1 ClH C(Me)═NOMe H CHO Z2.052 H H B1 Cl H H H OMe Z2.053 H H B1 Cl H Cl HOMe Z2.054 H H B1 Cl H Br H OMe Z2.055 H H B1 Cl H CF₃ H OMe Z2.056 H HB1 Cl H C≡C—H H OMe Z2.057 H H B1 Cl H C≡C—CH₂OMe H OMe Z2.058 H H B1 ClH C(Me)═NOMe H OMe Z2.059 H H B1 OMe H H H OMe Z2.060 H H B1 OMe H Cl HOMe Z2.061 H H B1 OMe H Br H OMe Z2.062 H H B1 OMe H CF₃ H OMe Z2.063 HH B1 OMe H C≡C—H H OMe Z2.064 H H B1 OMe H C≡C—CH₂OMe H OMe Z2.065 H HB1 OMe H C(Me)═NOMe H OMe Z2.066 H H B1 Me H H H Me Z2.067 H H B1 Me HCl H Me Z2.068 H H B1 Me H Br H Me Z2.069 H H B1 Me H I H Me Z2.070 H HB1 Me H CF₃ H Me Z2.071 H H B1 Me H C≡C—H H Me Z2.072 H H B1 Me H Me HMe Z2.073 H H B1 Me H C≡C—CH₂OMe H Me Z2.074 H H B1 Me H C(Me)═NOMe H MeZ2.075 H H B1 Me H NO₂ H Me Z2.076 H H B1 Me H NH₂ H Me Z2.077 H H B1 MeH NHCOMe H Me Z2.078 H H B1 Me H p-Cl-phenyl H Me Z2.079 H H B1 Me H H HCHO Z2.080 H H B1 Me H Cl H CHO Z2.081 H H B1 Me H Br H CHO Z2.082 H HB1 i-Pr H H H i-Pr Z2.083 H H B1 i-Pr H Cl H i-Pr Z2.084 H H B1 i-Pr HBr H i-Pr Z2.085 H H B1 t-Bu H H H t-Bu Z2.086 H H B1 t-Bu H Cl H t-BuZ2.087 H H B1 t-Bu H Br H t-Bu Z2.088 H H B1 t-Bu H Me H t-Bu Z2.089 H H81 t-Bu H t-Bu H t-Bu Z2.090 H H B1 t-Bu H OMe H t-Bu Z2.091 H H B1 Br HH H Br Z2.092 H H B1 Br H Br H Br Z2.093 H H B1 F H H H F Z2.094 H H B1F H Cl H F Z2.095 H H B1 F H Br H F Z2.096 H H B1 I H H H I Z2.097 H HB1 I H Cl H I Z2.098 Me H B1 H H COMe H H Z2.099 Me H B1 H F H F HZ2.100 Me H B1 Me H Cl H H Z2.101 Me H B1 H Cl Cl H H Z2.102 Me H B1 Ht-Bu H t-Bu H Z2.103 Me H B1 Cl H Cl H H Z2.104 Me H B1 Cl H H Cl HZ2.105 Me H B1 Cl H H H Cl Z2.106 Me H B1 H Cl Cl H H Z2.107 Me H B1 HCl H Cl H Z2.108 Me H B1 Cl H Cl H Cl Z2.109 Me H B1 Cl H Br H Cl Z2.110Me H B1 Cl H I H Cl Z2.111 Me H B1 Cl H CHF₂ H Cl Z2.112 Me H B1 Cl HCF₃ H Cl Z2.113 Me H B1 Cl H C≡C—H H Cl Z2.114 Me H B1 Cl H C≡C-Me H ClZ2.115 Me H B1 Cl H C≡C—Si(Me)₃ H Cl Z2.116 Me H B1 Cl H C≡C-t-Bu H ClZ2.117 Me H B1 Cl H C≡C—C-i-Pr H Cl Z2.118 Me H B1 Cl H C≡C—CH₂OMe H ClZ2.119 Me H B1 Cl H C≡C-p-Cl-phenyl H Cl Z2.120 Me H B1 Cl H p-Cl-phenylH Cl Z2.121 Me H B1 Cl H CHO H Cl Z2.122 Me H B1 Cl H CH═NOMe H ClZ2.123 Me H B1 Cl H COMe H Cl Z2.124 Me H B1 Cl H C(Me)═NOMe H Cl Z2.125Me H B1 Cl H NO₂ H Cl Z2.126 Me H B1 Cl H NH₂ H Cl Z2.127 Me H B1 Cl HNHMe H Cl Z2.128 Me H B1 Cl H N(Me)₂ H Cl Z2.129 Me H B1 Cl H NHCOMe HCl Z2.130 Me H B1 Cl H N═CHNEt(Me) H Cl Z2.131 Me H B1 Cl H OCF₃ H ClZ2.132 Me H B1 Cl H OCH₂CH═CHCl₂ H Cl Z2.133 Me H B1 Cl H p-Cl-phenoxy HCl Z2.134 Me H B1 Cl Me Cl H Cl Z2.135 Me H B1 Cl Cl Cl H Cl Z2.136 Me HB1 Cl H Cl Cl Cl Z2.137 Me H B1 Cl Cl Cl Cl Cl Z2.138 Me H B1 Cl H H HMe Z2.139 Me H B1 Cl H Cl H Me Z2.140 Me H B1 Cl H Br H Me Z2.141 Me HB1 Cl H CF₃ H Me Z2.142 Me H B1 Cl H C≡C—H H Me Z2.143 Me H B1 Cl HC≡C—CH₂OMe H Me Z2.144 Me H B1 Cl H C(Me)═NOMe H Me Z2.145 Me H B1 Cl HH H CHO Z2.146 Me H B1 Cl H Cl H CHO Z2.147 Me H B1 Cl H Br H CHO Z2.148Me H B1 Cl H CF₃ H CHO Z2.149 Me H B1 Cl H C≡C—H H CHO Z2.150 Me H B1 ClH C≡C—CH₂OMe H CHO Z2.151 Me H B1 Cl H C(Me)═NOMe H CHO Z2.152 Me H B1Cl H H H OMe Z2.153 Me H B1 Cl H Cl H OMe Z2.154 Me H B1 Cl H Br H OMeZ2.155 Me H B1 Cl H CF₃ H OMe Z2.156 Me H B1 Cl H C≡C—H H OMe Z2.157 MeH B1 Cl H C≡C—CH₂OMe H OMe Z2.158 Me H B1 Cl H C(Me)═NOMe H OMe Z2.159Me H B1 OMe H H H OMe Z2.160 Me H B1 OMe H Cl H OMe Z2.161 Me H B1 OMe HBr H OMe Z2.162 Me H B1 OMe H CF₃ H OMe Z2.163 Me H B1 OMe H C≡C—H H OMeZ2.164 Me H B1 OMe H C≡C—CH₂OMe H OMe Z2.165 Me H B1 OMe H C(Me)═NOMe HOMe Z2.166 Me H B1 Me H H H Me Z2.167 Me H B1 Me H Cl H Me Z2.168 Me HB1 Me H Br H Me Z2.169 Me H B1 Me H I H Me Z2.170 Me H B1 Me H CF₃ H MeZ2.171 Me H B1 Me H C≡C—H H Me Z2.172 Me H B1 Me H Me H Me Z2.173 Me HB1 Me H C≡C—CH₂OMe H Me Z2.174 Me H B1 Me H C(Me)═NOMe H Me Z2.175 Me HB1 Me H NO₂ H Me Z2.176 Me H B1 Me H NH₂ H Me Z2.177 Me H B1 Me H NHCOMeH Me Z2.178 Me H B1 Me H p-Cl-phenyl H Me Z2.179 Me H B1 Me H H H CHOZ2.180 Me H B1 Me H Cl H CHO Z2.181 Me H B1 Me H Br H CHO Z2.182 Me H B1i-Pr H H H i-Pr Z2.183 Me H B1 i-Pr H Cl H i-Pr Z2.184 Me H B1 i-Pr H BrH i-Pr Z2.185 Me H B1 t-Bu H H H t-Bu Z2.186 Me H B1 t-Bu H Cl H t-BuZ2.187 Me H B1 t-Bu H Me H t-Bu Z2.188 Me H B1 t-Bu H t-Bu H t-Bu Z2.189Me H B1 t-Bu H p-Cl-phenyl H t-Bu Z2.190 Me H B1 H H CF₃ H H Z2.191 Me HB1 H H Br H H Z2.192 Me H B1 Br H H H Br Z2.193 Me H B1 Br H Br H BrZ2.194 Me H B1 F H H H F Z2.195 Me H B1 F H Cl H F Z2.196 Me H B1 F H BrH F Z2.197 Me H B1 I H H H I Z2.198 Me H B1 I H Cl H I Z2.199 Me H B1 IH Br H I Z2.200 Me H B1 I H I H I Z2.201 Me Me B1 Cl H H H Cl Z2.202 MeMe B1 Cl H Cl H Cl Z2.203 Me Me B1 Br H H H Br Z2.204 Me Me B1 Br H Br HBr Z2.205 Me Me B1 Me H H H Me Z2.206 Me Me B1 Me H Cl H Me Z2.207 Me MeB1 Me H Br H Me Z2.208 Me H B1 Cl H H H Cl Z2.209 Et H B1 Me H H H MeZ2.210 Et H B1 Me H Br H Me Z2.211 H H B2 Cl H Cl H — Z2.212 H H B2 Cl HBr H — Z2.213 H H B2 Br H Br H — Z2.214 H H B2 Cl H CF₃ H — Z2.215 Me HB2 Cl H CF₃ H — Z2.216 Et H B2 Cl H CF₃ H — Z2.217 H Me B2 Cl H CF₃ H —Z2.218 Et H B2 Cl H CF₃ H — Z2.219 H H B3 Cl H H Cl — Z2.220 H H B3 Cl HH Br — Z2.221 H H B3 Cl H H I — Z2.222 H H B3 Cl H H Me — Z2.223 H H B3Me H H Cl — Z2.224 H H B3 Me H H Br — Z2.225 H H B3 Me H H Me — Z2.226Me H B3 Cl H H Cl — Z2.227 Me H B3 Me H H Cl — Z2.228 H H B4 Cl H H Cl —Z2.229 H H B4 Br H H Br — Z2.230 H H B4 Me H H Me — Z2.231 Me H B4 Cl HH Cl — Z2.232 Me H B4 Br H H Br — Z2.233 Me H B4 Me H H Me — Z2.234 H HB5 Me H Me — — Z2.235 H H B5 Me H Me — — Z2.236 H H B5 H Me H — — Z2.237H H B5 H Cl H — — Z2.238 H H B5 H Br H — — Z2.239 H H B5 H CF₃ H — —Z2.240 Me H B5 Me H Me — — Z2.241 Me H B5 Me H Me — — Z2.242 Me H B5 HMe H — — Z2.243 Me H B5 H Cl H — — Z2.244 Me H B5 H Br H — — Z2.245 Me HB5 H CF₃ H — — Z2.246 H H B20 Cl H H H H Z2.247 H H B20 Cl H Cl H HZ2.248 H H B20 Br H H H H Z2.249 H H B20 Br H Br H H Z2.250 H H B20 Me HH H H Z2.251 H H B20 CF₃ H H H H Z2.252 H H B20 COMe H H H H Z2.253 H HB20 Cl H H Cl H Z2.254 Me H B20 Cl H H H H Z2.255 Me H B20 Cl H Cl H HZ2.256 Me H B20 Br H H H H Z2.257 Me H B20 Br H Br H H Z2.258 Me H B20Me H H H H Z2.259 Me H B20 CF₃ H H H H Z2.260 Me H B20 COMe H H H HZ2.261 Me H B20 Cl H H Cl H Z2.262 H H B21 Cl H H H H Z2.263 H H B21 HCl H H H Z2.264 H H B21 Cl Cl H H H Z2.265 H H B21 H H H Cl H Z2.266 H HB21 Cl H H Cl H Z2.267 H H B21 H Cl H Cl H Z2.268 H H B21 Cl Cl H Cl HZ2.269 H H B21 Br H H H H Z2.270 H H B21 CF₃ H H H H Z2.271 H H B21 Me HH H H Z2.272 H H B21 Cl H H H H Z2.273 H H B21 Br H H Cl H Z2.274 H HB21 CF₃ H H Cl H Z2.275 H H B21 Me H H Cl H Z2.276 H H B21 Cl H H Cl HZ2.277 Me H B21 Cl H H H H Z2.278 Me H B21 H Cl H H H Z2.279 Me H B21 ClCl H H H Z2.280 Me H B21 H H H Cl H Z2.281 Me H B21 Cl H H Cl H Z2.282Me H B21 H Cl H Cl H Z2.283 Me H B21 Cl Cl H Cl H Z2.284 Me H B21 Br H HH H Z2.285 Me H B21 CF₃ H H H H Z2.286 Me H B21 Me H H H H Z2.287 Me HB21 Cl H H H H Z2.288 Me H B21 Br H H Cl H Z2.289 Me H B21 CF₃ H H Cl HZ2.290 Me H B21 Me H H Cl H Z2.291 Me H B21 Cl H H Cl H Z2.292 H H B22Me H H H H Z2.293 H H B22 H H H H Cl Z2.294 H H B22 Me H H H Cl Z2.295 HH B22 H H H Cl Cl Z2.296 H H B22 H H H NO₂ Cl Z2.297 H H B22 H H H Me ClZ2.298 H H B22 H H H H Br Z2.299 H H B22 H H H Cl Br Z2.300 H H B22 H HH Me Br Z2.301 H H B22 H H H Br Br Z2.302 Me H B22 Me H H H H Z2.303 MeH B22 H H H H Cl Z2.304 Me H B22 Me H H H Cl Z2.305 Me H B22 H H H Cl ClZ2.306 Me H B22 H H H NO₂ Cl Z2.307 Me H B22 H H H Me Cl Z2.308 Me H B22H H H H Br Z2.309 Me H B22 H H H Cl Br Z2.310 Me H B22 H H H Me BrZ2.311 Me H B22 H H H Br Br Z2.312 H H B23 Cl H H H H Z2.313 H H B23 ClCl H H H Z2.314 H H B23 Cl Me H H H Z2.315 H H B23 Me H H H H Z2.316 H HB23 Me Cl H H H Z2.317 H H B23 Me Me H H H Z2.318 H H B23 H H H H MeZ2.319 H H B23 Cl H H H Me Z2.320 H H B23 Me H H H Me Z2.321 Me H B23 ClH H H H Z2.322 Me H B23 Cl Cl H H H Z2.323 Me H B23 Cl Me H H H Z2.324Me H B23 Me H H H H Z2.325 Me H B23 Me Cl H H H Z2.326 Me H B23 Me Me HH H Z2.327 Me H B23 H H H H Me Z2.328 Me H B23 Cl H H H Me Z2.329 Me HB23 Me H H H Me Z2.330 H H B24 Cl H H H H Z2.331 H H B24 Br H H H HZ2.332 H H B24 CN H H H H Z2.333 H H B24 Me H H H H Z2.334 H H B24 OMe HH H H Z2.335 H H B24 Cl H Cl H H Z2.336 H H 824 Br H Cl H H Z2.337 H HB24 CN H Cl H H Z2.338 H H B24 Me H Cl H H Z2.339 H H B24 OMe H Cl H HZ2.340 H H B24 Cl H F H H Z2.341 H H B24 Br H F H H Z2.342 H H B24 CN HF H H Z2.343 H H B24 Me H F H H Z2.344 H H B24 OMe H F H H Z2.345 H HB24 Cl H H H F Z2.346 Me H B24 Cl H H H H Z2.347 Me H B24 Br H H H HZ2.348 Me H B24 CN H H H H Z2.349 Me H B24 Me H H H H Z2.350 Me H B24OMe H H H H Z2.351 Me H B24 Cl H Cl H H Z2.352 Me H B24 Br H Cl H HZ2.353 Me H B24 CN H Cl H H Z2.354 Me H B24 Me H Cl H H Z2.355 Me H B24OMe H Cl H H Z2.356 Me H B24 Cl H F H H Z2.357 Me H B24 Br H F H HZ2.358 Me H B24 CN H F H H Z2.359 Me H B24 Me H F H H Z2.360 Me H B24OMe H F H H Z2.361 Me H B24 Cl H H H F Z2.361 Me H B25 Me H H H H Z2.361Me H B25 Cl H H H H Z2.361 Me H B25 OMe H H H H Z2.361 Me H B26 Me H H HH Z2.361 Me H B26 Cl H H H H Z2.361 Me H B26 OMe H H H H Z2.361 Me H B28H H Me Me H Z2.361 Me H B28 Me Me Me Me H Z2.361 Me H B29 H H H Me MeZ2.361 Me H B29 Me Me H Me Me

Table 10 Compounds of Formula XXIV:

The invention is further illustrated by the preferred individualcompounds of formula (XXIV)

which are listed below in Table 10. Characterising data is given inTable 12.

TABLE 10 Cpd No. R₁ R₂ R₃ R₄ A Z3.1 H H H H3-difluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.2 Me H H H3-difluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.3 H H H H3-trifluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.4 Me H H H3-trifluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.5 H H H H3-trifluoromethyl-1-methyl-pyrrol-4-yl Z3.6 Me H H H3-trifluoromethyl-1-methyl-pyrrol-4-yl Z3.7 H H H H3-difluoromethyl-1-methyl-1H-triazol-4-yl Z3.8 Me H H H3-difluoromethyl-1-methyl-1H-triazol-4-yl Z3.9 H H H H3-trifluoromethyl-1-methyl-1H-triazol-4-yl Z3.10 Me H H H3-trifluoromethyl-1-methyl-1H-triazol-4-yl Z3.11 H H H H4-difluoromethyl-2-methyl-thiazol-5-yl Z3.12 Me H H H4-difluoromethyl-2-methyl-thiazol-5-yl Z3.13 H H H H4-trifluoromethyl-2-methyl-thiazol-5-yl Z3.14 Me H H H4-trifluoromethyl-2-methyl-thiazol-5-yl

Table 11 Compounds of Formula XXIIB

The invention is further illustrated by the preferred individualcompounds of formula (XXIIB)

which are listed below in Table 11. Characterising data is given inTable 12.

TABLE 11 Cpd No. R₁ R₂ R₃ R₄ X A Z3.1 H H H H —SO—3-difluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.2 Me H H H —SO—3-difluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.3 H H H H —SO—3-trifluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.4 Me H H H —SO—3-trifluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.5 H H H H —SO—3-trifluoromethyl-1-methyl-pyrrol-4-yl Z3.6 Me H H H —SO—3-trifluoromethyl-1-methyl-pyrrol-4-yl Z3.7 H H H H —SO—3-difluoromethyl-1-methyl-1H-triazol-4-yl Z3.8 Me H H H —SO—3-difluoromethyl-1-methyl-1H-triazol-4-yl Z3.9 H H H H —SO—3-trifluoromethyl-1-methyl-1H-triazol-4-yl Z3.10 Me H H H —SO—3-trifluoromethyl-1-methyl-1H-triazol-4-yl Z3.11 H H H H —SO—4-difluoromethyl-2-methyl-thiazol-5-yl Z3.12 Me H H H —SO—4-difluoromethyl-2-methyl-thiazol-5-yl Z3.13 H H H H —SO—4-trifluoromethyl-2-methyl-thiazol-5-yl Z3.14 Me H H H —SO—4-trifluoromethyl-2-methyl-thiazol-5-yl Z3.15 H H H H —SO₂—3-difluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.16 Me H H H —SO₂—3-difluoromethyl-1-methyl-1H-pyrazo1-4-yl Z3.17 H H H H —SO₂—3-trifluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.18 Me H H H —SO₂—3-trifluoromethyl-1-methyl-1H-pyrazol-4-yl Z3.19 H H H H —SO₂—3-trifluoromethyl-1-methyl-pyrrol-4-yl Z3.20 Me H H H —SO₂—3-trifluoromethyl-1-methyl-pyrrol-4-yl Z3.21 H H H H —SO₂—3-difluoromethyl-1-methyl-1H-triazol-4-yl Z3.22 Me H H H —SO₂—3-difluoromethyl-1-methyl-1H-triazol-4-yl Z3.23 H H H H —SO₂—3-trifluoromethyl-1-methyl-1H-triazol-4-yl Z3.24 Me H H H —SO₂—3-trifluoromethyl-1-methyl-1H-triazol-4-yl Z3.25 H H H H —SO₂—4-difluoromethyl-2-methyl-thiazol-5-yl Z3.26 Me H H H —SO₂—4-difluoromethyl-2-methyl-thiazol-5-yl Z3.27 H H H H —SO₂—4-trifluoromethyl-2-methyl-thiazol-5-yl Z3.28 Me H H H —SO₂—4-trifluoromethyl-2-methyl-thiazol-5-yl

Table 12: Characterising Data

Table 12 shows selected melting point and selected NMR data forcompounds of Tables 1 to 11. CDCl₃ was used as the solvent for NMRmeasurements, unless otherwise stated. If a mixture of solvents waspresent, this is indicated as, for example: CDCl₃/d₆-DMSO). No attemptis made to list all characterising data in all cases. LCMS-data forphysico-chemical characterization were obtained on an analytical WatersLC-MS instrument (W2790, ZMD-2000). Column was an Atlantis dC18, 3 um3.0 mm×20 mm. Solvents were: A=0.1% formic acid in water, B=0.1% formicacid in acetonitrile. Gradient was 10% to 90% B in 2.9 min; flow ratewas 1.7 ml/min. Physicochemical data are reported in the followingformat: retention time (min); M found in positive ionisation mode(m/z⁺).

In Table 12 and throughout the description that follows, temperaturesare given in degrees Celsius; “NMR” means nuclear magnetic resonancespectrum; MS stands for mass spectrum; “%” is percent by weight, unlesscorresponding concentrations are indicated in other units. The followingabbreviations are used throughout this description:

m.p. = melting point b.p. = boiling point. S = singlet br = broad d =doublet dd = doublet of doublets t = triplet q = quartet m = multipletppm = parts per million

TABLE 12 1H-NMR data: ppm Cpd No. (multiplicity/number of Hs) MS [M +H]⁺ m.p. (° C.) LCMS data 1.098 1.40(d, 3H, CH₃), 2.53(s, 3H, CH₃), 352resin — 3.90(s, 3H, CH₃), 4.05- 4.12(m, 2H, CH₂), 4.52- 4.57(m, 1H, CH),6.68(m_(broad), 1H, NH), 6.71- 6.98(t, 1H, CHF₂), 6.94- 6.97(d, 2H,Ar—H), 7.90- 7.94(m, 3H, 2H—Ar + 1H, pyrazole-H). 1.099 — — — 1.34 min;346 1.100 — — — 1.57 min; 358 1.101 — — — 1.59 min; 378 1.102 — — — 2.13min; 422 1.103 — — — 1.51 min; 378 1.104 (S)- 1.42 min; 378 enantiomere1.108 1.46-1.48(d, 3H), 3.93(s, 3H), 4.02- 412.6/414.5/416.5 124-126 —4.12(ddd, 2H), 4.49-4.55(m, 1H), 6.68(s, 1H) 6.76-7.03 (t, 1H), 7.31(s,2H), 7.88(s, 1H). 1.121 (S)- 1.30 min; 406 enantiomere 1.125 (S)- 1.72min; 423 enantiomere 1.132 (S)- 1.88 min; 502 enantiomere 1.137 (S)-1.87 min; 479 enantiomere 1.140 (S)- 1.64 min; 436 enantiomere 1.1661.46-1.48(d, 3H), 2.21(2s, 6H), 338 149-146 — 3.77-3.87(ddd, 2H),3.94(s, 3H), 4.47-4.53(m, 1H), 6.76-7.03(t, 1H), 6.79(s, 1H), 6.91(d,1H), 7.00(d, 2H), 7.93(s, 1H). 1.168 1.44-1.46(d, 3H), 2.21(2s, 6H),416/418 119-121 — 3.72-3.85(ddd, 2H), 3.89(s, 3H), 4.46-4.51(m, 1H),6.76(s, 1H), 6.77-7.03(t, 1H), 7.11(s, 1H), 7.93(s, 1H). 1.172 (S)- 1.52min; 352 enantiomere 1.180 (S)- 1.39 min; 386 enantiomere 1.182 (S)-1.80 min; 394 enantiomere 1.185 (S)- 2.02 min; 422 enantiomere 1.187(S)- 2.08 min; 436 enantiomere 1.188 (S)- 2.31 min; 478 enantiomere1.190 1.39-1.41(d, 3H), 3.91(s, 3H), 4.03- 378.6/379.7  99-102 —4.10(ddd, 2H), 4.51-4.57(m, 1H), 6.63(s, 1H) 6.66-7.93 (t, 1H), 6.98(d,2H), 7.53-7.55(d, 2H) 7.91(s, 1H). 1.191 1.30-1.32(d, 3H), 3.85(s, 3H),3.89- 388/390 106-108 — 3.95(ddd, 2H), 4.42-4.46(m, 1H), 6.59(s, 1H)6.73-6.86 (t, 1H), 6.74(d, 2H), 7.29-7.31 (d, 2H), 7.84(s, 1H). 1.1931.48-1.50(d, 3H), 3.93(s, 3H), 4.02- 543.8/545.7/549.8 122-124 —4.10(ddd, 2H), 4.52-4.55(m, 1H), 6.67(s, 1H) 6.78-7.05 (t, 1H), 7.64(s,2H), 7.88(s, 1H). 1.194 (S)- — — — 1.20 min; 346 enantiomere 1.221 — — —1.32 min; 356 1.239 1.39-1.41(d, 3H, CH₃), 3.91(s, 3H, CH₃), 413/415115-118 — 4.46-4.54(m, 2H, CH₂), 4.60- 4.66(m, 1H, CH), 6.63(s, 1H, NH),6.67-6.81(t, 1H, CHF₂), 7.85(d, 1H, Py- H), 7.90(s, 1H, pyrazole-H),8.30(t, 1H, Py-H). 1.565 88-90 1.649 110-114 1.650 113-116 1.651 108-1112.218 — — — 2.00 min; 374 2.565 121-123 2.649 130-132 2.651 resin 3.649134-136 4.565 109-110 4.649 151-153 5.565 534 resin 5.649 90-92 5.651resin Z1.108 — 254.5/256.5/258.5 waxy solid — free base Z1.166 — 190-193(S)-enantiomere HCl salt Z1.190 —   220.1 waxy solid — free base Z1.191— 230/232 waxy solid — free base Z1.193 — 389.8/391.8 waxy solid — freebase

Formulation Examples for Compounds of Formula I Example F-1.1 to F-1.2Emulsifiable Concentrates

Components F-1.1 F-1.2 compound of Tables 1 to 7 (1a to 7a) 25%  50%calcium dodecylbenzenesulfonate 5%  6% castor oil polyethylene glycolether 5% — (36 mol ethylenoxy units) tributylphenolpolyethylene glycolether —  4% (30 mol ethylenoxy units) cyclohexanone — 20% xylene mixture65%  20%

Emulsions of any desired concentration can be prepared by diluting suchconcentrates with water.

Example F-2 Emulsifiable Concentrate

Components F-2 compound of Tables 1 to 7 (1a to 7a) 10%octylphenolpolyethylene glycol ether  3% (4 to 5 mol ethylenoxy units)calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether  4% (36mol ethylenoxy units) cyclohexanone 30% xylene mixture 50%

Emulsions of any desired concentration can be prepared by diluting suchconcentrates with water.

Examples F-3.1 to F-3.4 Solutions

Components F-3.1 F-3.2 F-3.3 F-3.4 compound of Tables 1 to 7 (1a to 7a)80% 10% 5% 95% propylene glycol monomethyl ether 20% — — — polyethyleneglycol (relative molecular — 70% — — mass: 400 atomic mass units)N-methylpyrrolid-2-one — 20% — — epoxidised coconut oil — — 1%  5%benzin (boiling range: 160-190°) — — 94%  —

The solutions are suitable for use in the form of microdrops.

Examples F-4.1 to F-4.4 Granulates

Components F-4.1 F-4.2 F-4.3 F-4.4 compound of Tables 1 to 7 (1a to 7a)5% 10%  8% 21% kaolin 94%  — 79% 54% highly dispersed silicic acid 1% —13%  7% attapulgite — 90% — 18%

The novel compound is dissolved in dichloromethane, the solution issprayed onto the carrier and the solvent is then removed by distillationunder vacuum.

Examples F-5.1 and F-5.2 Dusts

Components F-5.1 F-5.2 compound of Tables 1 to 7 (1a to 7a) 2% 5% highlydispersed silicic acid 1% 5% talcum 97%  — kaolin — 90% 

Ready for use dusts are obtained by intimately mixing all components.

Examples F-6.1 to F-6.3 Wettable Powders

Components F-6.1 F-6.2 F-6.3 compound of Tables 1 to 7 (1a to 7a) 25% 50%  75% sodium lignin sulfonate 5% 5% — sodium lauryl sulfate 3% —  5%sodium diisobutylnaphthalene sulfonate — 6% 10% octylphenolpolyethyleneglycol ether — 2% — (7 to 8 mol ethylenoxy units) highly dispersedsilicic acid 5% 10%  10% kaolin 62%  27%  —

All components are mixed and the mixture is thoroughly ground in asuitable mill to give wettable powders which can be diluted with waterto suspensions of any desired concentration.

Example F7 Flowable Concentrate for Seed Treatment

compound of Tables 1 to 7 (1a to 7a) 40%  propylene glycol 5% copolymerbutanol PO/EO 2% tristyrenephenole with 10-20 moles EO 2%1,2-benzisothiazolin-3-one (in the form of a 20% 0.5%  solution inwater) monoazo-pigment calcium salt 5% Silicone oil (in the form of a75% emulsion in water) 0.2%  Water 45.3%  

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Biological Examples Fungicidal Actions Example B-1 Action AgainstBotrytis cinerea—Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds (0.002% active ingredient) into amicrotiter plate (96-well format) the nutrient broth containing thefungal spores is added. The test plates are incubated at 24° C. and theinhibition of growth is measured photometrically after 3-4 days. Theactivity of a compound is expressed as fungal growth inhibition (0=nogrowth inhibition, ratings of 80% to 99% mean good to very goodinhibition, 100%=complete inhibition).

Compounds 1.101, 1.166 and 1.193 show very good activity in this test(≦80% inhibition).

Compounds 1.221 and 1.239 show good activity in this test (50%inhibition).

Example B-2 Action Against Mycosphaerella arachidis (Early Leaf Spot ofGroundnut; Cercospora arachidicola [Anamorph])—Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds (0.002% active ingredient) into amicrotiter plate (96-well format) the nutrient broth containing thefungal spores is added. The test plates are incubated at 24° C. and theinhibition of growth is measured photometrically after 6-7 days. Theactivity of a compound is expressed as fungal growth inhibition (0=nogrowth inhibition, ratings of 80% to 99% mean good to very goodinhibition, 100%=complete inhibition).

Compounds 1.101, 1.166 (S)-enantiomere, 1.166 (racemat), 1.193, 1.221and 1.239 show very good activity in this test (≦30% inhibition).

Compounds 1.100, 1.102 and 1.103 show good activity in this test (≦50%inhibition).

Example B-3 Action Against Septoria tritici—Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds (0.002% active ingredient) into amicrotiter plate (96-well format) the nutrient broth containing thefungal spores is added. The test plates are incubated at 24° C. and theinhibition of growth is determined photometrically after 72 hrs. Theactivity of a compound is expressed as fungal growth inhibition (0=nogrowth inhibition, ratings of 80% to 99% mean good to very goodinhibition, 100%=complete inhibition).

Compounds 1.099, 1.101, 1.103, 1.166 (S)-enantiomere, 1.166 (racemat),1.193, 1.221 and 1.239 show very good activity in this test (≦80%inhibition).

Compound 1.102 shows good activity in this test (≦50% inhibition).

Example B-4 Action Against Tapesia yallundae—Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds (0.002% active ingredient) into amicrotiter plate (96-well format) the nutrient broth containing thefungal spores is added. The test plates are incubated at 24° C. and theinhibition of growth is measured photometrically after 6-7 days. Theactivity of a compound is expressed as fungal growth inhibition (0=nogrowth inhibition, ratings of 80% to 99% mean good to very goodinhibition, 100%=complete inhibition).

Compounds 1.101 and 1.102 show very good activity in this test (≦80%inhibition).

Example B-5 Action Against Monographella nivalis (Anamorph: Fusariumnivale, Microdochium nivale; Snow Mould)—Fungal Growth Assay

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing aDMSO-solution of the test compounds (0.002% active ingredient) into amicrotiter plate (96-well format) the nutrient broth containing thefungal spores is added. The test plates are incubated at 24° C. and theinhibition of growth is measured photometrically after 72 hrs (0=nogrowth inhibition, ratings of 80% to 99% mean good to very goodinhibition, 100%=complete inhibition).

Compounds 1.101, 1.102, 1.103, 1.166 (S)-enantiomere, 1.166 (racemat),1.193 and 1.221 show very good activity in this test (≦30% inhibition).

Compounds 1.099 and 1.239 show good activity in this test (≦50%inhibition).

Example B-6 Action Against Rhizoctonia solani—Fungal Growth Assay

Mycelial fragments of a newly grown liquid culture of the fungus aredirectly mixed into nutrient broth (PDB potato dextrose broth). Afterplacing a (DMSO) solution of the test compounds (0.002% activeingredient) into a microtiter plate (96-well format) the nutrient brothcontaining the fungal spores is added. The test plates are incubated at24° C. and the inhibition of growth is measured photometrically after3-4 days. The activity of a compound is expressed as fungal growthinhibition (0=no growth inhibition, ratings of 80% to 99% mean good tovery good inhibition, 100%=complete inhibition).

Compounds 1.166 (S)-enantiomere, 1.166 (racemat) and 1.193 show verygood activity in this test (≦80% inhibition).

Compound 1.101 shows good activity in this test (≦50% inhibition).

Example B-7 Action Against Phythophthora infestans (Late Blight) onTomato

Tomato leaf disks are placed on water agar in multiwell plates (24-wellformat) and sprayed with test solutions (0.02% active ingredient). Afterdrying, the leaf disks are inoculated with a spore suspension of thefungus. After appropriate incubation the activity of a compound isassessed 4 days after inoculation as preventive fungicidal activity.

Compounds 1.166 (S)-enantiomere and 1.166 (racemat) show good activityin this test (≦550% inhibition).

Example B-8 Action Against Botrvtis cinera (Grey Mold) on Beans

Bean leaf disks are placed on agar in multiwell plates (24-well format)and sprayed with test solutions (0.02% active ingredient). After drying,the leaf disks are inoculated with a spore suspension of the fungus.After appropriate incubation the activity of a compound is assessed 3days after inoculation as preventive fungicidal activity.

Compounds 1.099, 1.166 (S)-enantiomere, 1.166 (racemat), 1.193, 1.221and 1.239 show very good activity in this test (≦80% inhibition).

Compound 1.101 shows good activity in this test (≦50% inhibition).

Example B-9 Action Against Erysiphe graminis F.Sp. Tritici (WheatPowdery Mildew)

Wheat leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions (0.02% active ingredient). Afterdrying, the leaf disks are inoculated with a spore suspension of thefungus. After appropriate incubation the activity of a compound isassessed 7 days after inoculation as preventive fungicidal activity.

Compounds 1.166 (S)-enantiomere, 1.166 (racemat), 1.193, 1.221 and 1.239show very good activity in this test (≦80% inhibition).

Compound 1.103 shows good activity in this test (≦50% inhibition).

Example B-10 Protective Action Against Puccinia recondita (Brown Rust)on Wheat

Wheat leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions (0.02% active ingredient). Afterdrying, the leaf disks are inoculated with a spore suspension of thefungus. After appropriate incubation the activity of a compound isassessed 8 days after inoculation as preventive fungicidal activity.

Compounds 1.166 (S)-enantiomere, 1.166 (racemat) and 1.193 show verygood activity in this test (≦80% inhibition).

Compounds 1.101 and 1.221 show good activity in this test (≦50%inhibition).

Example B-11 Curative Action Against Puccinia recondita (Brown Rust) onWheat

Wheat leaf segments are placed on agar in multiwell plates (24-wellformat) and inoculated with a spore suspension of the fungus. One dayafter inoculation the leaf segments are sprayed with test solutions(0.02% active ingredient). After appropriate incubation the activity ofa compound is assessed 8 days after inoculation as curative fungicidalactivity.

Compounds 1.166 (S)-enantiomere, 1.166 (racemat) and 1.193 show verygood activity in this test (≦80% inhibition).

Example B-12 Action Against Pyricularia oryzae (Rice Blast) on Rice

Rice leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions (0.02% active ingredient). Afterdrying, the leaf disks are inoculated with a spore suspension of thefungus. After appropriate incubation the activity of a compound isassessed 5 days after inoculation as preventive fungicidal activity.

Compounds 1.166 (S)-enantiomere and 1.166 (racemat) show good activityin this test (≦50% inhibition).

Example B-13 Action Against Leptosphaeria nodorum (Septoria nodorum;Glume Blotch) on wheat

Wheat leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions (0.02% active ingredient). Afterdrying, the leaf disks are inoculated with a spore suspension of thefungus. After appropriate incubation the activity of a compound isassessed 4 days after inoculation as preventive fungicidal activity.

Compounds 1.098, 1.101, 1.166 (S)-enantiomere, 1.166 (racemat), 1.193and 1.221 show good activity in this test (≦50% inhibition).

Example B-14 Action Against Pyrenophora teres (Net Blotch) on Barley

Barley leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions (0.02% active ingredient). Afterdrying, the leaf disks are inoculated with a spore suspension of thefungus. After appropriate incubation the activity of a compound isassessed 4 days after inoculation as preventive fungicidal activity.

Compounds 1.100, 1.101, 1.103, 1.166 (S)-enantiomere, 1.166 (racemat),1.193, 1.221 and 1.239 show very good activity in this test (≦80%inhibition).

Compounds 1.099 and 1.102 show good activity in this test (≦50%inhibition).

1. A compound of the formula I

wherein A is a 5-membered heterocyclic ring containing one to threeheteroatoms, each independently selected from oxygen, nitrogen andsulphur, the heterocyclic ring being substituted by the groups R₅, R₆and R₇; R₅, R₆ and R₇ are each, independently, hydrogen, halogen, cyano,nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy(C₁-C₄alkyl) or C₁-C₄halogenalkoxy(C₁-C₄alkyl), provided thatat least one of R₅, R₆ and R₇ is not hydrogen; R₁, R₂, R₃ and R₄independently of each other are hydrogen, halogen, C₁-C₆alkyl,C₁-C₆halogenalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆halogenalkoxy,C₁-C₆alkylthio or C₁-C₆halogenalkylthio; or R₁ and R₂ together are aC₂-C₅alkylene group, which is unsubstituted or substituted by one ormore C₁-C₆alkyl groups; or R₁ and R₃ together are a C₁-C₅alkylene group,which is unsubstituted or substituted by one or more C₁-C₆alkyl groups;or R₃ and R₄ together are a C₂-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups; R₁₅ is hydrogen orC₃-C₇cycloalkyl; B is phenyl, naphthyl or a 5- to 10-memberedheteroaromatic ring system containing one to three heteroatoms, eachindependently selected from oxygen, nitrogen and sulphur, the phenyl,naphthyl or 5- to 10-membered heteroaromatic ring system beingsubstituted by one or more substituents R₈; each substituent R₈independently of each other stands for halogen, C₁-C₆alkoxy, —C(O)H,C₁-C₆alkylcarbonyl, amino, C₁-C₆alkylamino, di-C₁-C₆alkyl-amino,C₁-C₆alkylcarbonylamino, C₁-C₆haloalkoxy, C₁-C₆haloalkylthio, cyano,nitro, —C(R^(a))═N(OR^(b)), —N═C(R^(e))—N(R^(f))₂, C₁-C₆alkyl, which isunsubstituted or substituted by one or more substituents R₉,C₂-C₆alkenyl, which is unsubstituted or substituted by one or moresubstituents R₉, C₂-C₆alkynyl, which is unsubstituted or substituted byone or more substituents R₉, C₂-C₆alkenyloxy, which is unsubstituted orsubstituted by one or more substituents R₉, C₃-C₆cycloalkyl, which isunsubstituted or substituted by one or more substituents R₉,C₆-C₁₄bicycloalkyl, which is unsubstituted or substituted by one or moresubstituents R₉, phenyl, which is unsubstituted or substituted by one ormore substituents R₉, or phenyloxy, which is unsubstituted orsubstituted by one or more substituents R₉; each R₉ is independently ofeach other halogen, nitro, C₃-C₆cycloalkyl, C₁-C₆alkoxy,C₁-C₆halogenalkoxy, C₁-C₆alkylthio, C₁-C₆halogenalkylthio,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenyl, halophenyl,tri-C₁-C₆alkyl-silyl or —C(R^(c))═N(OR^(d)); each R^(a), R^(c), R^(e)and R^(f) is independently of each other hydrogen or C₁-C₆alkyl; eachR^(b) and R^(d) is independently of each other C₁-C₆alkyl; andtautomers/isomers/enantiomers of these compounds.
 2. A compound offormula I according to claim 1, wherein R₁₅ is hydrogen.
 3. A compoundof formula I according to claim 1, wherein A is a 5-memberedheterocyclic ring containing one to three heteroatoms, eachindependently selected from oxygen, nitrogen and sulphur; theheterocyclic ring being substituted by the groups R₆, R₇ and R₈.
 4. Acompound of formula I according to claim 1, wherein A is A₁

in which R₁₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; R₁₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; and R₁₈ is hydrogen, halogen or cyano; orA is A₂

in which R₂₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; and R₂₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; or A is A₃

in which R₃₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; R₃₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; and R₃₈ is hydrogen, halogen or cyano; orA is A₄

in which R₄₆ and R₄₇ independently of one another are halogen, cyano,nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl.
 5. A compoundof formula I according to claim 1, wherein R₁ is methyl; and R₂, R₃ andR₄ are hydrogen.
 6. A compound of formula I according to claim 1,wherein B is selected from

in which R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ each independently of each otherstands for hydrogen, halogen, C₁-C₆alkoxy, —C(O)H, C₁-C₆alkylcarbonyl,amino, C₁-C₆alkylamino, di-C₁-C₆alkyl-amino, C₁-C₆alkylcarbonylamino,C₁-C₆haloalkoxy, C₁-C₆haloalkylthio, cyano, nitro, —C(R^(a))═N(OR^(b)),—N═C(R^(e))—N(R^(f))₂, C₁-C₆alkyl, which is unsubstituted or substitutedby one or more substituents R₉, C₂-C₆alkenyl, which is unsubstituted orsubstituted by one or more substituents R₉, C₂-C₆alkynyl, which isunsubstituted or substituted by one or more substituents R₉,C₂-C₆alkenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉, C₃-C₆cycloalkyl, which is unsubstituted or substitutedby one or more substituents R₉, C₆-C₁₄bicycloalkyl, which isunsubstituted or substituted by one or more substituents R₉, phenyl,which is unsubstituted or substituted by one or more substituents R₉, orphenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉; each R₉ is independently of each other halogen, nitro,C₃-C₆cycloalkyl, C₁-C₆alkoxy, C₁-C₆halogenalkoxy, C₁-C₆alkylthio,C₁-C₆halogenalkylthio, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenyl,halophenyl, tri-C₁-C₆alkyl-silyl or —C(R^(c))═N(OR^(d)); each R^(a),R^(c), R^(e) and R^(f) is independently of each other hydrogen orC₁-C₆alkyl; each R^(b) and R^(d) is independently of each otherC₁-C₆alkyl; provided that at least one of R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ isnot hydrogen.
 7. A compound of formula I according to claim 1, wherein Bis B₁

in which R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ each independently of each otherstands for hydrogen, halogen, C₁-C₆alkoxy, —C(O)H, C₁-C₆alkylcarbonyl,amino, C₁-C₆alkylamino, di-C₁-C₆alkyl-amino, C₁-C₆alkylcarbonylamino,C₁-C₆haloalkoxy, C₁-C₆haloalkylthio, cyano, nitro, —C(R^(a))═N(OR^(b)),—N═C(R^(e))—N(R^(f))₂, C₁-C₆alkyl, which is unsubstituted or substitutedby one or more substituents R₉, C₂-C₆alkenyl, which is unsubstituted orsubstituted by one or more substituents R₉, C₂-C₆alkynyl, which isunsubstituted or substituted by one or more substituents R₉,C₂-C₆alkenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉, C₃-C₆cycloalkyl, which is unsubstituted or substitutedby one or more substituents R₉, C₆-C₁₄bicycloalkyl, which isunsubstituted or substituted by one or more substituents R₉, phenyl,which is unsubstituted or substituted by one or more substituents R₉, orphenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉; each R₉ is independently of each other halogen, nitro,C₃-C₆cycloalkyl, C₁-C₆alkoxy, C₁-C₆halogenalkoxy, C₁-C₆alkylthio,C₁-C₆halogenalkylthio, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenyl,halophenyl, tri-C₁-C₆alkyl-silyl or —C(R^(c))═N(OR^(d)); each R^(a),R^(c), R^(e) and R^(f) is independently of each other hydrogen orC₁-C₆alkyl; each R^(b) and R^(d) is independently of each otherC₁-C₆alkyl; provided that at least one of R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ isnot hydrogen.
 8. A compound of formula I according to claim 1, wherein Bis B_(1A)

in which R₁₀, R₁₂ and R₁₄ each independently of each other stands forhydrogen, halogen, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆haloalkylthio,—C(R^(a))═N(OR^(b)), C₁-C₆alkyl, which is unsubstituted or substitutedby one or more substituents R₉, C₂-C₆alkenyl, which is unsubstituted orsubstituted by one or more substituents R₉, C₂-C₆alkynyl, which isunsubstituted or substituted by one or more substituents R₉, phenyl,which is unsubstituted or substituted by one or more substituents R₉;phenyloxy, which is unsubstituted or substituted by one or moresubstituents R₉; and each R₉ is independently of each other halogen orC₁-C₆alkoxy; provided that at least one of R₁₀, R₁₂ and R₁₄ is nothydrogen.
 9. A compound according to claim 8, in which R₁₀, R₁₂ and R₁₄each independently of each other stands for hydrogen, halogen,C₁-C₆alkyl or C₁-C₆haloalkyl; provided that at least one of R₁₀, R₁₂ andR₁₄ is not hydrogen.
 10. A compound of formula II

wherein B, R₁, R₂, R₃ and R₄ are each as defined in claim
 1. 11. Acompound of formula IV

wherein B is as defined in claim 1; R₁, R₃ and R₄ independently of eachother are hydrogen, C₁-C₆ alkyl, C₁-C₆ halogenalkyl, C₃-C₆cycloalkyl,C₂-C₆alkenyl, C₂-C₆ haloalkenyl, C₂-C₆alkynyl, C₂-C₆ haloalkynyl, C₁-C₆alkoxy, C₁-C₆ halogenalkoxy, C₁-C₆ alkylthio or C₁-C₆ halogenalkylthio;or R₁ and R₃ together are a C₂-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups; or R₃ and R₄ togetherare a C₂-C₅alkylene group, which is unsubstituted or substituted by oneor more C₁-C₆alkyl groups.
 12. A compound of formula XXIV

wherein A is as defined in claim 1; and R₁, R₂, R₃ and R₄ independentlyof each other are hydrogen, C₁-C₆ alkyl, C₁-C₆ halogenalkyl,C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆ haloalkenyl, C₂-C₆alkynyl or C₂-C₆haloalkynyl; or R₁ and R₂ together are a C₂-C₅alkylene group, which isunsubstituted or substituted by one or more C₁-C₆alkyl groups; or R₁ andR₃ together are a C₂-C₅alkylene group, which is unsubstituted orsubstituted by one or more C₁-C₆alkyl groups; or R₃ and R₄ together area C₂-C₅alkylene group, which is unsubstituted or substituted by one ormore C₁-C₆alkyl groups.
 13. A compound of formula XXIIB

wherein A is as defined in claim 1; X₁ is —S(O)— or —S(O)₂—; and R₁, R₂,R₃ and R₄ independently of each other are hydrogen, C₁-C₆ alkyl, C₁-C₆halogenalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl,C₂-C₆alkynyl or C₂-C₆ haloalkynyl; or R₁ and R₂ together are aC₂-C₅alkylene group, which is unsubstituted or substituted by one ormore C₁-C₆alkyl groups; or R₁ and R₃ together are a C₂-C₅alkylene group,which is unsubstituted or substituted by one or more C₁-C₆alkyl groups;or R₃ and R₄ together are a C₂-C₅alkylene group, which is unsubstitutedor substituted by one or more C₁-C₆alkyl groups.
 14. A method ofcontrolling or preventing infestation of plants by phytopathogenicmicroorganisms, wherein a compound of formula I according to claim 1, isapplied to the plants, to parts thereof or the locus thereof.
 15. Acomposition for controlling and protecting against phytopathogenicmicroorganisms, comprising a compound of formula I according to claim 1and an inert carrier.